Doped sol-gel materials and method of manufacture utilizing reduced mixing temperatures

ABSTRACT

A method of preparing a solution for forming a doped gel monolith includes providing a first substance including a metal alkoxide. The method further includes providing a second substance including a catalyst. The method further includes providing a chemical including a dopant. The method further includes forming a solution including the dopant, said forming including mixing the first substance and the second substance together. The method further includes cooling the solution to a mixture temperature which is at or below zero degrees Celsius, wherein the solution has a significantly longer gelation time at the mixture temperature than at room temperature.

CLAIM OF PRIORITY

[0001] This application is a continuation-in-part of, and claimspriority from, U.S. Utility Patent Application No. 10/117,921, filedApr. 5, 2002, which is a continuation-in-part of, and claims priorityfrom, U.S. Utility patent application Ser. No. 09/974,725, filed Oct. 9,2001, both of which are incorporated in their entirety by referenceherein.

BACKGROUND OF THE INVENTION

[0002] 1. Field of the Invention

[0003] This invention relates to pure and doped sol-gel materials andprocesses for fabricating glass and ceramic monoliths with selectedproperties (e.g., chemical purity, homogeneity) compatible with avariety of applications, including high-performance optical systems.

[0004] 2. Description of the Related Art

[0005] High-performance oxide-based materials are increasingly in demandfor use in a variety of optical applications. For example, silica glasshas the optical transmittance, mechanical hardness, chemical durability,thermal stability, low thermal expansion, and high laser damagethreshold which make it an optimal material for applications such asoptoelectronic laser diodes, fiber optic telecommunications, medicallaser delivery systems, and military optical sensors. There issignificant pressure on manufacturers to find materials and fabricationtechniques which can satisfy the increasingly stringent performancerequirements of these and other high-performance optical systems.

[0006] Numerous techniques are currently in use for the fabrication ofglasses or ceramics. For example, silica glasses have traditionally beenmanufactured by melting natural quartz or synthetic silica in cruciblesat high temperatures (typically about 1700° C.-2000° C.). However, theresultant materials have limited utility for various opticalapplications, primarily due to structural inhomogeneities as well asimpurity concentrations (e.g., from intrinsic impurities in the rawmaterials, incomplete chemical reactions of components, andcontamination by the crucible). Such high-temperature processes are alsounsuitable for manufacturing products with certain compositions,tailored dopant or additive gradients, organic or high vapor pressureadditives, or additives in their metallic or partially reduced states.

[0007] Another more recent technique for manufacturing silica glasseshas been chemical vapor deposition (CVD), in which silicon-containingchemical vapors are combined with oxygen under high temperatureconditions to deposit silica onto a substrate. However, the resultantmaterials are relatively expensive due to low material collectionefficiencies, slow processing rates, and complex processing andpollution control equipment. Furthermore, CVD processes lack theversatility for fabricating more compositionally complex glasses.

[0008] Sol-gel technology has been used to fabricate products whichsatisfy some or all of the desired performance requirements without thedifficulties or limitations found in more conventional fabricationtechniques. A typical sol-gel silica process involves the transition ofa liquid colloidal solution “sol” phase into a solid porous “gel” phase,followed by drying and consolidating (i.e., sintering) the resulting gelmonolith at elevated temperatures to form silica glass. One method ofpreparing a silica porous gel monolith is to pour into a mold a solutionof silica-forming compounds (e.g., silicon alkoxides), solvents, andcatalysts, which then undergoes hydrolysis and polymerization, resultingin a wet porous gel monolith or matrix. After drying the wet gelmonolith in a controlled environment to remove the fluid from the pores,the dry gel monolith is densified into a solid glass-phase monolith.

[0009] Sol-gel technology can yield products with the desired chemicalpurity, homogeneity, and flexibility in compositions, dopants, anddopant profiles. However, the potential for sol-gel processes forfabricating large monoliths has been limited by various problems. Largegel monoliths can take a long time to dry, thereby limiting the productthroughput. But even more importantly, shrinkage of the gel monolithduring the drying process often results in cracking, especially inlarger gel monoliths.

[0010] As outlined by Pope, et al. in U.S. Pat. No. 5,023,208 and Wang,et al. in U.S. Pat. No. 5,264,197, both of which are incorporated byreference herein, this resultant cracking of gel monoliths during thedrying step of the fabrication process is believed to result fromstresses due to capillary forces in the gel pores. Numerous techniquesfor reducing this cracking have been proposed, and many of these effortshave focused on increasing the pore sizes of the gel monolith to reducethe capillary stresses generated during drying. Pope, et al. disclosessubjecting the gel to a hydrothermal aging treatment which causes silicamonomers to migrate from small pores to silica particle surfaces in theporous gel matrix, thereby increasing the average pore diameter. Wang,et al. discloses adjusting the relative concentrations of an alcoholdiluent and/or one or more catalysts such as HCl or HF, which has theeffect of increasing the average pore radius of the resulting dry gel.HF catalyzed gels generally have larger pore sizes than gels catalyzedby other catalysts such as HCl, HNO₃, H₂SO₄, or oxalic acid.

SUMMARY OF THE INVENTION

[0011] According to one aspect of embodiments of the present invention,a method of preparing a solution for forming a doped gel monolithcomprises providing a first substance comprising a metal alkoxide. Themethod further comprises providing a second substance comprising acatalyst. The method further comprises providing a chemical comprised ofa dopant. The method further comprises forming a solution comprising thedopant, said forming comprising mixing the first substance and thesecond substance together. The method further comprises cooling thesolution to a mixture temperature which is at or below zero degreesCelsius, wherein the solution has a significantly longer gelation timeat the mixture temperature than at room temperature.

[0012] According to another aspect of embodiments of the presentinvention, a method processes a solution comprising a catalyst, water,metal alkoxide, and a chemical comprised of a dopant. The methodcomprises extending a gelation time of the solution by keeping thesolution at a predetermined temperature at or below zero degreesCelsius.

[0013] According to another aspect of embodiments of the presentinvention, an optical preform comprises a plurality of materialcomponents including a core material and a cladding material. Acomponent of the optical preform is manufactured by a process comprisingproviding a first substance comprising a metal alkoxide. The processfurther comprises providing a second substance comprising a catalyst.The process further comprises providing a chemical comprised of adopant. The process further comprises forming a solution comprising thedopant, the forming comprising mixing the first substance and the secondsubstance together. The process further comprises cooling the solutionto a mixture tempareture at or below zero degree Celsius, wherein thesolution has a significantly longer gelation time at the mixturetemperature than at room temperature.

[0014] According to another aspect of embodiments of the presentinvention, a method of forming a doped gel monolith comprises providinga first substance comprising a metal alkoxide. The method furthercomprises providing a second substance comprising a catalyst. The methodfurther comprises providing a chemical comprised of a dopant, thechemical being substantially free of fluorine-containing alkoxide. Themethod further comprises forming a solution substantially free offlourine-containing alkoxide and comprising the dopant, the formingcomprising mixing the first substance and the second substance together.The method further comprises cooling the solution to a mixturetemperature substantially below room temperature, wherein the solutionhas a significantly longer gelation time at the mixture temperature thanat room temperature. The method further comprises allowing the solutionto gel, thereby forming the doped gel monolith.

[0015] According to another aspect of embodiments of the presentinvention, an optical preform comprises a plurality of materialcomponents including a core material and a cladding material. Acomponent of the optical preform is manufactured by a process comprisingproviding a first substance comprising a metal alkoxide. The processfurther comprises providing a second substance comprising a catalyst.The process further comprises providing a chemical comprised of adopant, the chemical being substantially free of flourine-containingalkoxide. The process further comprises forming a solution substantiallyfree of fluorine-containing alkoxide and comprising the dopant, theforming comprising mixing the first substance and the second substancetogether. The process further comprises cooling the solution to amixture temperature substantially below room temperature, wherein thesolution has a significantly longer gelation time at the mixturetemperature than at room temperature. The process further comprisesallowing the solution to gel, thereby forming a gel monolith.

BRIEF DESCRIPTION OF THE DRAWINGS

[0016] This aspect and other aspects of embodiments of the presentinvention will be apparent to the skilled artisan from the followingdetailed description read in conjunction with the appended drawings,which are meant to illustrate, and not to limit, the invention, and inwhich:

[0017]FIG. 1 is a flow diagram of a method of forming a gel monolith inaccordance with an embodiment of the present invention.

[0018]FIG. 2 is a flow diagram corresponding to another embodiment ofthe present invention in which the first solution is formed by mixingmetal alkoxide with a solvent and cooling the first solution.

[0019] FIGS. 3A-3F schematically illustrate various embodiments of thepresent invention in which the first solution is mixed and cooled.

[0020]FIG. 4 is a flow diagram corresponding to another embodiment ofthe present invention in which the second solution is formed by mixingthe catalyst with water and cooling the second solution.

[0021]FIG. 5 is a flow diagram corresponding to another embodiment ofthe present invention in which the metal alkoxide is cooled to a firsttemperature, the second solution is formed by mixing the catalyst,solvent, and water, and cooling the second solution.

[0022]FIG. 6 is a flow diagram corresponding to another embodiment ofthe present invention in which the third solution is formed by mixingthe first solution and the second solution, and cooling the thirdsolution.

[0023]FIG. 7 schematically illustrates a mixing station in accordancewith embodiments of the present invention.

[0024]FIG. 8 schematically illustrates an alternative mixing station inaccordance with embodiments of the present invention.

[0025]FIG. 9 is a flowchart of a procedure for preparing components of amold for casting in accordance with embodiments of the presentinvention.

[0026]FIG. 10 schematically illustrates an exploded view of a mold forforming a gel monolith in accordance with embodiments of the presentinvention.

[0027] FIGS. 11A-11D schematically illustrate interim stages during theformation of the gel monolith using the mold of FIG. 10 in accordancewith an embodiment of the present invention.

[0028] FIGS. 12A-12C schematically illustrate interim stages during theformation of the gel monolith using the mold of FIG. 11 in accordancewith an embodiment of the present invention.

[0029]FIG. 13 schematically illustrates an exploded view of a mold inaccordance with other embodiments of the present invention.

[0030] FIGS. 14A-14E schematically illustrate interim stages during theformation of the gel monolith using the mold of FIG. 13 in accordancewith embodiments of the present invention.

[0031]FIGS. 15A and 15B schematically illustrate two molds in accordancewith embodiments of the present invention.

[0032]FIG. 16 is a flow diagram of a method of forming a gel monolithhaving a first gel portion and a second gel portion in accordance withembodiments of the present invention.

[0033]FIG. 17 schematically illustrates a gel monolith formed by amethod in accordance with embodiments of the present invention.

[0034]FIG. 18 schematically illustrates a sol-gel-derived rod formed bya method in accordance with embodiments of the present invention.

[0035]FIG. 19 schematically illustrates a gel monolith comprising poresfilled with liquid, an inner region, and an outer region.

[0036]FIG. 20 is a flow diagram of a method of processing a gel monolithin accordance with embodiments of the present invention.

[0037]FIG. 21 schematically illustrates a temporal temperature profilecompatible with embodiments of the present invention.

[0038]FIG. 22 is a flow diagram of an embodiment of removing a portionof the liquid from the pores of the gel monolith.

[0039]FIG. 23 is a flow diagram of an embodiment of removingsubstantially all of the remaining liquid from the pores of the gelmonolith.

[0040] FIGS. 24A-24C schematically illustrate temporal temperatureprofiles comprising cycles in accordance with embodiments of the presentinvention.

[0041]FIG. 25 schematically illustrates an exemplary temporaltemperature profile in accordance with embodiments of the presentinvention.

[0042]FIG. 26 graphically illustrates five pore diameter distributionsin accordance with embodiments of the present invention.

[0043]FIG. 27 is a flow diagram of a consolidating process in accordancewith embodiments of the present invention.

[0044] FIGS. 28A-C schematically illustrate prior art depositionprocesses for forming optical fiber preforms.

[0045]FIG. 28D schematically illustrates a prior art drawing process forforming optical fiber from an optical fiber preform.

[0046]FIG. 29 is a flow diagram of a method of forming an optical fiberpreform in accordance with embodiments of the present invention.

[0047] FIGS. 30A-30E schematically illustrate interim stages of formingthe optical fiber preform.

[0048]FIGS. 31A and 31B are flow diagrams of alternative embodiments ofthe method of forming the optical fiber preform.

[0049]FIGS. 32A and 32B are flow diagrams of additional alternativeembodiments of the method of forming the optical fiber preform.

[0050]FIG. 33 schematically illustrates the dependence of the refractiveindex of fluorine-doped silica glass as a function of fluorineconcentration for an exemplary system.

[0051]FIG. 34 is a flow diagram of a method of preparing a solution forforming a doped gel monolith in accordance with embodiments of thepresent invention.

[0052] FIGS. 35A-C are flow diagrams of alternative embodiments offorming a third solution comprising the dopant-containing chemical.

[0053]FIG. 36 is a flow diagram of a method of forming a doped gelmonolith in accordance with embodiments of the present invention. FIG.37 is a flow diagram of a method of forming a tubular gel monolith inaccordance with embodiments of the present invention.

[0054]FIG. 38 is a flow diagram of a method of preparing a sol-gelsolution for forming a tubular gel monolith in accordance withembodiments of the present invention.

DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENT

[0055] Preparing a Solution

[0056] During the drying of a large gel monolith, the gel monolithshrinks in size, and capillary forces in the gel pores arise as theliquid content of the gel monolith is reduced. The tendency of gelmonoliths to develop cracks is dependent on these capillary forces. Forexample, U.S. patent application Ser. No. 09/615,628 by Wang, et al.,entitled “Sol-Gel Process for Production of Oxide-Based Glass andCeramic Articles,” which is incorporated by reference herein, disclosesa process that reduces the influence of these forces. The processcomprises removing liquid from the pores of the gel monolith such thatthe outer region of the gel monolith is not dried before the innerregion of the gel monolith is dried, thereby avoiding inhomogeneities inthe capillary forces which cause stresses and cracking of the gelmonolith.

[0057] Because the magnitude of the capillary forces is a function ofthe sizes of the pores in the gel monolith, the tendency for cracking ofgel monoliths may be reduced by tailoring the gel microstructure so asto produce gel monoliths with larger pore sizes. The microstructure of agel monolith is influenced by the rates of hydrolysis and ofpolymerization which occur simultaneously during the gelation of the wetgel monolith from the sol. For example, in the case of a silica-basedsol in which tetraethylorthosilicate or TEOS (Si(OCH₂H₅)₄) is mixed withdeionized water, a diluent or solvent such as ethyl alcohol or ethanol(C₂H₅OH), and a catalyst such as HF or ammonia, hydrolysis occurs withthe following reaction: Si(OC₂H₅)₄+4H₂O→4C₂H₅OH+Si(OH)₄. The Si(OH)₄molecules polymerize, resulting in a network of SiO₂ and water. Numerousfactors influence the kinetics of hydrolysis and polymerization,including the type and concentration of any catalysts and thetemperature profile. The influence of the catalyst concentration on thepore sizes of the resultant gel monoliths is illustrated by Wang, et al.in U.S. Pat. No. 5,264,197. Wang, et al. disclose that increasing the HFcatalyst concentration, while maintaining constant concentrations ofother constituents of the sol, results in an increase in the averagepore radius of the resulting dry gel.

[0058] Catalysts such as HF or ammonia increase the rate of hydrolysisand polymerization. If the catalyst concentration is too high, thehydrolysis and polymerization reactions are so fast that the gelationtime is extremely short, and in certain circumstances can be nearlyinstantaneous. Gelation time as used herein is defined as the time fromthe moment a sol comprising water and a silicon-containing material suchas TEOS, along with the other constituents of the sol, is prepared tothe moment the sol forms a gel which does not flow. Very short gelationtimes do not provide sufficient time to allow a prepared sol to befiltered, poured into molds for casting, eventual gelation, and furtherprocessing. In addition, bubbles which form during the gelation processmay not have an opportunity to diffuse out of the gel if the gelationtime is short, thereby degrading the quality of the resulting gel.Furthermore, higher temperatures have the effect of shortening thegelation time even further.

[0059]FIG. 1 is a flow diagram of a method 100 of forming a gel monolithin accordance with an embodiment of the present invention. While theflow diagram of FIG. 1 illustrates a particular embodiment with steps ina particular order, other embodiments with different orders of steps arealso compatible with the present invention.

[0060] In the embodiment described in FIG. 1, in an operational block110, a first solution 10 is prepared, the first solution 10 comprisingmetal alkoxide. Examples of metal alkoxides compatible with embodimentsof the present invention include, but are not limited to, siliconalkoxides (such as tetramethylorthosilicate (TMOS) ortetraethylorthosilicate (TEOS)), germanium alkoxides (such astetraethoxygermane (TEOG)), aluminum alkoxides, zirconium alkoxides, andtitanium alkoxides. In certain embodiments, the first solution 10comprises more than one metal alkoxide (e.g., both TEOS and TEOG). Incertain embodiments, the first solution 10 further comprises a solvent.Examples of solvents include, but are not limited to, ethyl alcohol,methyl alcohol, or other alcohols.

[0061] In an operational block 120, a second solution 20 is prepared,the second solution 20 comprising a catalyst. Examples of catalystsinclude, but are not limited to, hydrofluoric acid (HF) and ammonia(NH₃). In certain embodiments, the second solution 20 further comprisesa solvent, examples of which include, but are not limited to ethylalcohol, methyl alcohol, or other alcohols.

[0062] In an operational block 130, a third solution 30 is prepared bymixing the first solution 10 and the second solution 20 together. Whilein certain embodiments, the second solution 20 further comprises water,in other embodiments, water is added to the third solution 30 such thatthe third solution 30 thereby comprises water and metal alkoxide. Thethird solution 30 can then begin to undergo the hydrolysis andpolymerization reactions which form the gel. The presence of thecatalyst in the third solution 30 accelerates the formation of the gel(i.e., reduces the gelation time of the third solution 30 as compared tothe gelation time without the catalyst) as described above. In anoperational block 140, at least one of the first solution 10, secondsolution 20, and third solution 30 is cooled to achieve a mixturetemperature for the third solution which is substantially below roomtemperature. In certain embodiments, only the third solution 30 iscooled to achieve a mixture temperature which is substantially belowroom temperature. Such a mixture temperature serves to decelerate theformation of the gel, such that the third solution 30 has asignificantly longer gelation time at the mixture temperature ascompared to a room temperature gelation time for the third solution 30.In this way, cooling the third solution 30 to the mixture temperaturemakes it possible to increase the catalyst concentration in the thirdsolution 30 while reducing the problematic effects associated withhigher catalyst concentrations. In an operational block 150, the thirdsolution 30 is allowed to gel, thereby forming the gel monolith.

[0063] In certain embodiments, as illustrated in the flow diagram ofFIG. 2, preparing 110 the first solution 10 comprises an operationalblock 112 in which metal alkoxide is mixed with a solvent to form thefirst solution 10 and an operational block 114 in which the firstsolution 10 is cooled to a first temperature substantially below roomtemperature. While FIG. 2 illustrates a particular embodiment in whichmixing 112 occurs before cooling 114, in other embodiments one or bothof the mixed constituents of the first solution 10 (i.e., the metalalkoxide and the solvent) can be cooled before or while being mixedtogether to form the first solution 10.

[0064] In certain embodiments, mixing 112 the metal alkoxide with thesolvent is achieved by pouring both constituents of the first solution10 into a first vessel 11. In other embodiments, a mixing system 12 isused to agitate the first solution 10 to ensure sufficiently homogeneousmixing of the metal alkoxide and the solvent. Examples of mixing systems12 in accordance with embodiments of the present invention include, butare not limited to, magnetic stirrers, mechanical stirrers, staticmixers, or other mechanisms to agitate the first solution 10. In theembodiment schematically illustrated in FIG. 3A, the mixing system 12comprises a magnetic stirrer which includes a stir bar 13 comprising aferromagnetic material and a magnetic driver 14 coupled to the stir bar13. Upon activation, the magnetic driver 14 generates magnetic forces tospin the stir bar 13 within the first solution 10 for a predeterminedperiod of time. In other embodiments, as schematically illustrated inFIG. 3C (discussed more fully below), the mixing system 12 comprises amechanical stirrer 15 which is inserted into the first solution 10,activated to agitate the first solution 10 for a predetermined period oftime, then removed from the first solution 10.

[0065] In certain embodiments, the first temperature is preferablyapproximately equal to or less than 0° C., more preferably approximatelyequal to or less than −10° C., still more preferably approximately equalto or less than −25° C., and most preferably approximately equal to orless than −40° C. In certain embodiments in which the first temperatureis approximately equal to or less than 0° C., the first solution 10 canbe cooled in a first vessel 11 placed in an ice bath 16 comprising amixture of water and ice, as schematically illustrated in FIG. 3A. Instill other embodiments, the first solution 10 can be cooled in a firstvessel 11 contained within a refrigerator 17, as schematicallyillustrated in FIG. 3B. One example of a refrigerator 17 compatible withembodiments of the present invention is an Isotemp General Purpose LabRefrigerator available from Fisher Scientific International of Hampton,N.H.

[0066] In certain embodiments in which the first temperature isapproximately equal to or less than −10° C., the first solution 10 canbe cooled in a first vessel 11 placed in a glycol bath 18 comprising amixture of propylene glycol or ethylene glycol and water, typically inapproximately equal proportions. In certain embodiments, asschematically illustrated in FIG. 3C, the glycol bath 18 is coupled to achiller 19 which removes heat from the glycol bath 18 to maintain thedesired first temperature. One example of a chiller 19 compatible withembodiments of the present invention is an RTE-140 Low Temperature BathCirculator from Thermo Neslab of Portsmouth, N.H. In other embodimentsin which the first temperature is approximately equal to or less than−25° C., the first solution 10 can be cooled in a first vessel 11contained within a freezer 22, as schematically illustrated in FIG. 3D.One example of a freezer 22 compatible with embodiments of the presentinvention is an Isotemp General Purpose Lab Freezer available fromFisher Scientific International of Pittsburgh, Pa.

[0067] In certain embodiments in which the first temperature isapproximately equal to or less than −40° C., the first solution 10 canbe cooled in a first vessel 11 placed in a dry ice bath 23 comprising amixture of dry ice (CO₂), propylene glycol or ethylene glycol, andwater, as schematically illustrated in FIG. 3E. Typically, the dry icebath 23 comprises equal amounts of propylene glycol or ethylene glycol,and water, and a sufficient amount of dry ice to reduce the temperatureof the dry ice bath 23 to the desired level. In certain embodiments, afreezer 22 can be used to reach temperatures equal to or less than −40°C., as schematically illustrated in FIG. 3D. One example of a freezer 22compatible with embodiments of the present invention is an ULT-80 UltraLow Temperature Bath Circulator from Thermo Neslab of Portsmouth, N.H.In other embodiments, the first solution 10 can be cooled by bubblingnitrogen vapor 24 from a liquid nitrogen reservoir 25 through the firstsolution 10, as schematically illustrated in FIG. 3F.

[0068] As illustrated in the flow diagram of FIG. 4, in certainembodiments, preparing 120 the second solution 20 comprises anoperational block 122 in which the catalyst is mixed with water to formthe second solution 20 and an operational block 124 in which the secondsolution 20 is cooled to a second temperature substantially below roomtemperature. While FIG. 4 illustrates a particular embodiment in whichmixing 122 occurs before cooling 124, in other embodiments one or bothof the mixed constituents of the second solution 20 (i.e., the catalystand the water) are cooled before or while being mixed together.

[0069] In certain embodiments, mixing 122 the catalyst with water isachieved by pouring both constituents of the second solution 20 into asecond vessel. Similarly to the mixing 112 of the metal alkoxide withthe solvent to form the first solution 10, in other embodiments, astirring system can be used to agitate the second solution 20 to ensuresufficiently homogeneous mixing of the catalyst and water. Examples ofstirring systems in accordance with embodiments of the present inventioninclude, but are not limited to, magnetic stirrers, mechanical stirrers,static mixers, or other mechanisms to agitate the second solution 20.

[0070] In certain embodiments, the second temperature is preferablyapproximately equal to or less than 0° C., more preferably approximatelyequal to or less than −10° C., still more preferably approximately equalto or less than −25° C., and most preferably approximately equal to orless than −40° C. In certain embodiments in which the second temperatureis approximately equal to or less than 0° C., the second solution 20 canbe cooled in the second vessel placed in an ice bath 16 or contained ina refrigerator 17, as described above in relation to the cooling of thefirst solution 10. Similarly, in embodiments in which the secondtemperature is approximately equal to or less than −10° C., a glycolbath 18 and chiller 19 can be used, in embodiments in which the secondtemperature is approximately equal to or less than −25° C., a freezer 22can be used, and in embodiments in which the second temperature isapproximately equal to or less than −40° C., a dry ice bath 23 or afreezer 22 can be used. In addition, in other embodiments, the secondsolution 20 can be cooled by bubbling nitrogen vapor 24 from a liquidnitrogen reservoir 25 through the second solution 20.

[0071] In certain embodiments, the first solution 10 can comprise metalalkoxide and the second solution 20 can comprise the catalyst, solvent,and water. In such an embodiment, as illustrated in the flow diagram ofFIG. 5, preparing 110 the first solution 10 comprises cooling the metalalkoxide to a first temperature substantially below room temperature inan operational block 116. In such an embodiment, preparing 120 thesecond solution 20 comprises mixing the catalyst, solvent, and water toform the second solution 20 in an operational block 126, and cooling thesecond solution 20 to a second temperature substantially below roomtemperature in an operational block 128. Embodiments such as thatillustrated in FIG. 5 avoid having the water freeze which would inhibitsufficient mixing and further processing of the gel monolith, forexample in embodiments in which the second temperature is approximatelyequal to or less than −25° C. Other embodiments for preparing the firstsolution 10 and second solution 20 include other procedures for coolingthe first solution 10 and second solution 20 without freezing any of theconstituents.

[0072] As illustrated in the flow diagram of FIG. 6, in certainembodiments, preparing 130 the third solution 30 comprises anoperational block 132 in which the first solution 10 is mixed with thesecond solution 20 to form the third solution 30. In certainembodiments, mixing 132 the first solution 10 and second solution 20 isachieved by pouring both solutions 10, 20 into a third vessel 55.Alternatively in other embodiments, the first solution 10 is maintainedat a temperature substantially below room temperature while beingtransferred to the third vessel 55 via a material measurement system 60.

[0073] As schematically illustrated in FIG. 7, the material measurementsystem 60 of certain embodiments comprises an input valve 62, ameasuring vessel 64, a scale 66, and an output valve 68. In certainembodiments, the input valve 62 is adjustable and coupled to aproportional-integral-differential (PID) controller (not shown) tocontrol the flow of the first solution 10 into the measuring vessel 64.The scale 66 of certain embodiments is a weight scale which provides ameasure of the amount of the first solution 10 in the measuring vessel64. Alternatively, in other embodiments, the scale 66 measures the totalvolume of the first solution 10 in the measuring vessel 64. The outputvalve 68 of certain embodiments is coupled to a solenoid (not shown)which opens and closes the output valve 68 in response to signals. Incertain embodiments, the second solution 20 is transferred to the thirdvessel 55 via a second material measurement system 70. The secondmaterial measurement system 70 can be similar to the materialmeasurement system 60 for the first solution 10, i.e., comprising asecond input valve 72, a second measuring vessel 74, a second scale 76,and a second output valve 78, as schematically illustrated in FIG. 7.Other embodiments of the material measurement system 60 do not comprisea scale 66 or a second scale 76. Furthermore, in still otherembodiments, the first solution 10 and the second solution 20 can bemetered directly into the third vessel 55, thereby avoiding themeasuring vessels 64, 74.

[0074] Similarly to the mixing 112 of the metal alkoxide with thesolvent to form the first solution 10, in other embodiments, a stirringsystem can be used to agitate the third solution 30 to ensuresufficiently homogeneous mixing of the first solution 10 and secondsolution 20. Examples of stirring systems in accordance with embodimentsof the present invention include, but are not limited to, magneticstirrers, mechanical stirrers, static mixers, or other mechanisms toagitate the third solution 30.

[0075] At least one of the first solution 10, second solution 20, andthird solution 30 is cooled 140 to achieve a mixture temperature for thethird solution 30 which is substantially below room temperature. Asillustrated in an operational block 142 of FIG. 6, in certainembodiments, the third solution 30 is cooled 142 to the mixturetemperature concurrently with mixing 132 the first solution 10 with thesecond solution 20. In the embodiment schematically illustrated in FIG.7, the third vessel 55 is in a glycol bath 18 coupled to a chiller 19 tomaintain the third solution 30 at a temperature substantially below roomtemperature during mixing. While FIG. 6 illustrates a particularembodiment in which mixing 132 occurs concurrently with cooling 142, inother embodiments cooling 140 the third solution 30 occurs after mixing132, or one or both of the mixed constituents of the third solution 30(i.e., the first solution 10 or the second solution 20) are cooledbefore being mixed together.

[0076] Once the first solution 10 and the second solution 20 are mixedtogether, the metal alkoxide of the first solution 10 and the water ofthe second solution 20 begin to undergo exothermic hydrolysis andpolymerization reactions which result in the formation of the gelmonolith. The presence of a catalyst, such as HF, increases the reactionrates of these hydrolysis and polymerization reactions, thereby reducingthe gelation time. With the temperature of the third solution 30increasing due to the exothermic reactions, the reaction rates of thesereactions increase even further, thereby reducing the gelation time evenfurther. As described above, due to the combination of high catalystconcentrations and increased heat from the exothermic reactions, thehydrolysis and polymerization reaction rates can become too fast (i.e.,the gelation time is too short) to allow sufficient processing of thegel monolith resulting from the third solution 30. Therefore, inembodiments of the present invention in which the third solution 30comprises a catalyst, the third solution 30 is cooled 142 to a mixturetemperature substantially below room temperature concurrently with themixing 132 to reduce the heat available to the hydrolysis andpolymerization reactions and to slow down the kinetics of thesereactions. At the mixture temperature, the third solution 30 has alonger gelation time as compared to its gelation time at roomtemperature.

[0077] In certain embodiments, the mixture temperature is preferablyapproximately equal to or less than 0° C., more preferably approximatelyequal to or less than −10° C., still more preferably approximately equalto or less than −25° C., and most preferably approximately equal to orless than −40° C. In certain other embodiments, the third solution 30 iscooled to a mixture temperature at which the gelation time of the thirdsolution 30 is increased by at least ten times as compared to thegelation time of the third solution 30 at room temperature. In certainembodiments in which the mixture temperature is approximately equal toor less than 0° C., the third solution 30 can be cooled using an icebath 16 or a refrigerator 17, as described above in relation to thecooling of the first solution 10. Similarly, in embodiments in which themixture temperature is approximately equal to or less than −10° C., aglycol bath 18 and chiller 19 can be used, in embodiments in which themixture temperature is approximately equal to or less than −25° C., afreezer 22 can be used, and in embodiments in which the mixturetemperature is approximately equal to or less than −40° C., a dry icebath 23 or a freezer 22 can be used. In addition, in other embodiments,the third solution 30 can be cooled by bubbling nitrogen vapor 24 from aliquid nitrogen reservoir 25 through the third solution 30.

[0078] In certain embodiments, the third solution 30 is allowed to gel,thereby forming the gel monolith, as illustrated in the operationalblock 150 of the flow diagram of FIG. 1. The cooled third solution 30 ispoured into a mold 75 in certain embodiments, where the hydrolysis andpolymerization reactions are allowed to continue so that the thirdsolution 30 gels into the gel monolith. In certain other embodiments,the third solution 30 is prepared by mixing the first solution 10 andsecond solution 20, filtering the resultant third solution 30,transferring the third solution 30 into the mold 75, and cooling thethird solution 30 in the mold 75 while the third solution 30 continuesto gel to form the gel monolith.

[0079] In still other embodiments, as schematically illustrated in FIG.7, the third solution 30 is transferred from the third vessel into aseries of molds 75 at approximately 20° C. via cooled pumps 80 andcooled filters 90. In certain embodiments, the pumps 80 are eithercooled or insulated to prevent the temperatures of the third solution 30from increasing while flowing to the molds 75. One example of a pump 80compatible with embodiments of the present invention is Type NumberUND1.300TT.18, available from KNF Neuberger, Inc. of Trenton, N.J.

[0080] The filters 90 remove particles from the third solution 30 whichwould degrade the quality of the resultant gel monolith. These particlescan be contaminants or can be due to pre-gelling of small amounts of thethird solution 30. In certain embodiments, each filter 90 comprisesmultiple filters, which can be chosen to remove particles within certainsize ranges. For example, a filter 90 can comprise a 0.6 μm filterconnected in series with a 0.05 μm filter. Filters of other sizes ofparticles are also compatible with embodiments of the present invention.In certain embodiments, the filters 90 are cooled or insulated toprevent the temperatures of the third solution 30 from increasing whileflowing therethrough. Exemplary filters 90 compatible with embodimentsof the present invention are available from Millipore Corporation ofBedford, Mass.

[0081]FIG. 8 schematically illustrates a mixing station 300 compatiblewith embodiments of the present invention in which the first solution 10and second solution 20 are each prepared in a first vessel 310 andsecond vessel 320, respectively. In the embodiment schematicallyillustrated in FIG. 8, the first vessel 310 is cooled by a first glycolbath 312 which is maintained at a first temperature by a chiller 314.Similarly, the second vessel 320 is cooled by a second glycol bath 322which is maintained at a second temperature by a chiller 324. In certainother embodiments, the first temperature and second temperature areapproximately equal, and the first solution 10 and second solution 20are cooled to the same temperature by a single bath. In addition, asdescribed above, other types of baths or cooling procedures to reducethe temperatures of the first solution 10 and second solution 20 are inaccordance with embodiments of the present invention.

[0082] In certain embodiments, the first vessel 310 is coupled to astatic mixer 330 via a first fluid conduit 331 comprising a first valve332 and a first pump 333, and the second vessel 320 is coupled to thestatic mixer 330 via a second fluid conduit 334 comprising a secondvalve 335 and a second pump 336. As schematically illustrated in FIG. 8,the first solution 10 is pumped through the first fluid conduit 331 fromthe first vessel 310 by the first pump 333 upon opening the first valve332. Similarly, the second solution 20 is pumped through the secondfluid conduit 334 from the second vessel 320 by the second pump 336 uponopening the second valve 335. In certain such embodiments, the mixingstation 300 is configured to match the pressure drops along the firstfluid conduit 331 and second fluid conduit 334 (e.g., by pressurizingthe first vessel 310 and second vessel 320). In certain embodiments, thefirst fluid conduit 331 and second fluid conduit 334 are either cooledor insulated to prevent the temperatures of either the first solution 10or second solution 20 from increasing while flowing to the static mixer330.

[0083] Certain embodiments comprise an in-line static mixer 330, asschematically illustrated in FIG. 8, which has various mixing elementsto generate vortices as the fluid flows through the static mixer 330,thereby providing an efficient mixing of the fluids flowingtherethrough. Exemplary static mixers 330 compatible with embodiments ofthe present invention are available from Cole-Parmer Instrument Companyof Vernon Hills, Ill. In certain embodiments, the static mixer 330 iseither cooled or insulated to prevent the temperature of the thirdsolution 30 from increasing while being mixed in the static mixer 330.

[0084] In the embodiment schematically illustrated in FIG. 8, the mixingstation 300 further comprises a cooling coil 340 coupled to the staticmixer 330 via a third pump 342. In certain embodiments, the cooling coil340 is a thin-walled tube placed in a third glycol bath 344 which iscoupled to a third chiller 345. The thin walls of the cooling coil 340permit heat transfer from the third solution 30 to the third glycol bath344, thereby achieving a mixture temperature for the third solution 30substantially below room temperature. In addition, as described above,other types of baths or cooling procedures to reduce the mixturetemperature of the third solution 30 are in accordance with embodimentsof the present invention.

[0085] In the embodiment schematically illustrated in FIG. 8, the mixingstation 300 comprise a filter 350 coupled to the cooling coil 340. Incertain embodiments, the filter 350 comprises multiple filters, whichcan be chosen to remove particles within certain size ranges. Forexample, the filter 350 can comprise a 0.6 μm filter connected in serieswith a 0.05 μm filter. In certain embodiments, the filter 350 is cooledor insulated to prevent the temperatures of the third solution 30 fromincreasing while flowing therethrough. Exemplary filters 350 compatiblewith embodiments of the present invention are available from MilliporeCorporation of Bedford, Mass.

[0086] In the embodiment schematically illustrated in FIG. 8, the thirdsolution 30 flows through the filter 350 to the mold 360, which is in afourth glycol bath 362 coupled to a fourth chiller 363. Alternatively inother embodiments, the mold 360 is at approximately room temperature.Once in the mold 360, the third solution 30 is permitted to gel, therebyforming the gel monolith. In addition, as described above, other typesof baths or cooling procedures to reduce the temperature of the thirdsolution 30 are in accordance with embodiments of the present invention.

[0087] In certain other embodiments, because of the corrosive nature ofthe constituents of the third solution 30 (e.g., the hydrogen fluoridecatalyst), some or all of the components of the mixing station 300 havetheir internal portions coated with a protective material. Examples ofprotective materials in accordance with embodiments of the presentinvention include, but are not limited to, Teflon® available from E. I.DuPont de Nemours & Co. of Wilmington, Del. or Kynar® available from ElfAtochem North America of Philadelphia, Pa.

[0088] In certain other embodiments, some or all of the valves, pumps,and chillers are controlled by a control system comprising amicroprocessor. In response to user input, the control system canregulate the timing and duration of the flow of the first solution 10,second solution 20, and third solution 30, as well as the temperaturesof these solutions.

[0089] By preparing the third solution 30 at a mixture temperaturesubstantially below room temperature, embodiments of the presentinvention allow higher percentages of catalyst in the third solution 30without having gelation times which inhibit further processing of thegel monolith. For example, the gelation time for a third solution 30comprising approximately 3.7 mole % of HF at room temperature is on theorder of 100 to 200 seconds. Typically, a gelation time greater thanapproximately 5 minutes is required to pour the third solution 30 into amold and to permit bubbles to diffuse out of the third solution 30,thereby avoiding difficulties in the processing of the gel monolith.When processing larger quantities of solution (e.g., during productionruns), the time required to process the solution can be even longer.However, by preparing the same third solution 30 comprisingapproximately 3.7 mole % of HF at −14° C., the gelation time is on theorder of 10 to 30 minutes. By preparing the third solution 30 at −40°C., the third solution 30 can comprise approximately 10 mole % of HFbefore the gelation time is shortened to 10 minutes.

[0090] As described above, higher percentages of the catalyst result inlarger pore sizes in the resultant gel monolith, thereby reducing thecapillary stresses generated during drying of the gel monolith. Forexample, a third solution 30 comprising approximately 3.7 mole % of HFresults in a gel monolith with pore sizes of approximately 500 Å, whilea third solution 30 comprising approximately 7.4 mole % of HF results ina gel monolith with pore sizes of approximately 1150 Å.

[0091] In certain embodiments, the third solution 30 comprisespreferably greater than approximately 3 mole % of a catalyst, morepreferably greater than 4 mole % of a catalyst, and most preferablygreater than 10 mole % of a catalyst. These catalyst concentrations areaccompanied in certain embodiments by solvent concentrations in thethird solution 30 of approximately 0.5 mole % or less. In certainembodiments, the third solution 30 comprising greater than approximately3 mole % of the catalyst is cooled to have a gelation time greater thanapproximately five minutes. In certain other embodiments, the thirdsolution 30 comprising greater than approximately 3 mole % of a catalystis cooled to have a gelation time greater than one hour. In still otherembodiments, the third solution 30 comprising greater than approximately3 mole % of a catalyst is cooled to have a gelation time greater thantwo hours.

[0092] Monoliths produced using chemical-vapor deposition techniquestypically have pore diameter distributions which range fromapproximately 1000 Å to 2000 Å (i.e., with standard deviations ofapproximately 500 Å). In certain embodiments, the third solution 30 canresult in gel monoliths with pore diameter distributions with mean porediameters between approximately 400 Å and approximately 1600 Å, but withsmaller ranges of diameters than those obtained using chemical-vapordeposition techniques, as described more fully below.

[0093] In an exemplary embodiment, a first solution 10 comprisingapproximately 900 grams of TEOS, approximately 117 grams of TEOG, andapproximately 440 grams of ethanol is prepared and stored in a freezer22 at a temperature of approximately −30° C. for approximately 20 hours.A second solution 20 comprising approximately 110 grams of ethanol,approximately 165 grams of water, and approximately 50 grams of a 49% HF(51% water) solution is also prepared and stored in the freezer 22 at atemperature of approximately −30° C. for approximately 20 hours. Thefirst solution 10 and the second solution 20 are then mixed togetherusing a magnetic stirrer in a vessel in a glycol bath 18 coupled to achiller 19 whereby the temperature of the resultant third solution 30 ismaintained between approximately −10° C. and −15° C. After mixing for aminimum of approximately five minutes, the third solution 30 is pumpedinto a mold 75 through a filter 80 comprising a 0.6 μm filter and a 0.05μm filter. The mold 75 is then moved to a flat and safe area atapproximately room temperature where the third solution 30 sits andforms a gel monolith. After the third solution 30 forms the gelmonolith, ethanol is poured onto the gel monolith to prevent crackingdue to the reaction heat generated inside the gel monolith body. All thesteps of this exemplary embodiment are performed in a class 1000 orbetter clean room environment in which the temperature is maintained atapproximately 60° to 70° F. and the humidity is between approximately35% and 55%.

[0094] Prior to casting the gel monolith, the mold used for the castingis cleaned in certain embodiments to avoid any materials or particulatematter which could degrade the resultant gel monolith and could createbubbles between the gel monolith and the mold which would be potentialstress points for cracking. Such cleaning procedures are alsoparticularly important for embodiments in which a good surface finish ofthe gel monolith is desired.

[0095]FIG. 9 is a flowchart of a procedure 370 for preparing componentsof a mold for casting in accordance with embodiments of the presentinvention. In certain embodiments, the procedure 370 is performed in aClass 1000 (or lower) clean room to reduce the possibility ofparticulate contamination of the mold prior to casting the gel monolith.In an operational block 372, the components of the mold are chemicallycleaned. In an operational block 374, the components of the mold arephysically cleaned. In an operational block 376, the components of themold are dried. In an operational block 378, the components of the moldhave any static charge neutralized.

[0096] In certain embodiments of the operational block 372, chemicallycleaning the mold components comprises soaking the components in a HFsolution and rinsing the components with deionized water. In certainsuch embodiments, a cleaning vessel is provided and visually inspectedto ensure that it is free of residue such as dried gel, particles, dust,etc. The cleaning vessel is then filled to a desired level with acleaning solution comprising deionized water and hydrofluoric acid (HF).In certain embodiments, the HF:H₂O ratio is approximately 1:10. The moldcomponents are then soaked in the cleaning solution for at leastapproximately 8 hours to remove residual material from the surfaces ofthe mold components. The mold components are then soaked in a firstrinsing vessel containing deionized water for approximately 30 minutesto remove HF which has adhered to the surfaces of the mold componentsand are then soaked in a second rinsing vessel containing deionizedwater for approximately 5 minutes. The mold is then filled briefly withdeionized water which is then dumped out.

[0097] In certain embodiments of the operational block 374, physicallycleaning the mold components comprises ultrasonically cleaning the moldcomponents. Certain mold components are filled with deionized water andplaced in an ultrasonic cleaner for approximately 30 minutes, and arethen emptied. A final rinse with deionized water is then performed.

[0098] In certain embodiments of the operational block 376, drying themold components comprises allowing water to evaporate from the surfacesof the mold components. In certain embodiments of the operational block378, neutralizing the static charge on the mold components comprisesexposing the mold components to an anti-static air flow from a filteredair gun for approximately 10 to 15 seconds. A static meter can be usedto ensure that the mold components are no longer statically charged. Inaddition, a particle counter can be utilized to detect particles withinthe mold. After the procedure 370, non-static, lint-free material can beused to completely cover the cleaned mold components until they are usedfor casting. Other embodiments of the procedure 370 for preparing moldcomponents for casting are compatible with embodiments of the presentinvention.

[0099] Casting A Gel Monolith

[0100]FIG. 10 schematically illustrates an exploded view of a mold 400for forming a gel monolith 402 comprising a first gel portion 404 and asecond gel portion 406 in accordance with embodiments of the presentinvention. FIGS. 11A-11D schematically illustrate interim stages duringthe formation of the gel monolith 402 in accordance with an embodimentof the present invention. The mold 400 comprises a base 410 comprising afirst hydrophobic surface 412. The mold 400 further comprises a tubularouter wall 420 comprising a second hydrophobic surface 422 and the outerwall 420 is coupled to the base 410. The mold 400 further comprises aremovable tubular insert 430 comprising an inner surface 431 and anouter hydrophobic surface 432 and the insert 430 is removably coupled tothe base 410.

[0101] In certain embodiments, the first hydrophobic surface 412 of thebase 410 comprises polytetrafluoroethylene (PTFE) (e.g., Teflon®), whilein other embodiments, the first hydrophobic surface 412 comprisespolymethylpentene (PMP), polystyrene (PS), or other hydrophobicmaterials. In addition, the first hydrophobic surface 412 in certainembodiments has a good surface finish (i.e., it is polished andsufficiently defect-free) to provide resultant glass surfaces whichconform to the desired specifications. Certain embodiments can utilize atapered first hydrophobic surface 412 to facilitate removal of the gelmonolith 402 from the mold 400. The first hydrophobic surface 412 ofsuch embodiments can be tapered from the tubular outer wall 420 to thetubular insert 430, and can be flat or have a curvature (e.g.,spherical).

[0102] The base 410 can be fabricated entirely from these materials,thereby providing the first hydrophobic surface 412 of such embodiments.Alternatively, the base 410 can comprise other materials which have acoating of a hydrophobic material (e.g., PTFE, PMP, or PS) on one ormore surfaces, thereby forming the first hydrophobic surface 412. Incertain such embodiments, the base 410 accompanies the gel monolith 402through additional processing steps, so the materials comprising thebase 410 are able to withstand the various temperatures, pressures, andexposure to various corrosive compounds (e.g., HF, TEOS, Ge) to whichthe base 410 is subjected during the formation of the gel monolith 402.As is described more fully below, the base 410 is shaped so as to coupleto the outer wall 420 and to the insert 430. In addition, the base 410of certain embodiments is removably coupled to the outer wall 420 so asto facilitate cleaning of the mold 400 and removal of the gel monolith402 from the mold 400.

[0103] In certain embodiments, as schematically illustrated in FIG. 10,the base 410 further comprises a first base portion 414 and a secondbase portion 416, or alternatively, the first base portion 414 and athird base portion 418. The first base portion 414 is coupled to theouter wall 420 and comprises the first hydrophobic surface 412, a cavity413, and a mating surface 419. The cavity 413 extends from the firsthydrophobic surface 412 to the mating surface 419. The second baseportion 416 comprises a tubular projection 415 adapted to couple to theinsert 430 and to the mating surface 419 of the first base portion 414with the tubular projection 415 coupled to the cavity 413. The thirdbase portion 418 comprises a solid projection 417 adapted to couple tothe mating surface 419 with the solid projection 417 filling the cavity413.

[0104] The second base portion 416 and third base portion 418 can eachbe interchangeably removably coupled to the first base portion 414. Asis explained more fully below, when coupled to the first base portion414, the second base portion 416 and third base portion 418 providealternative versions of the base 410 compatible with various stages ofthe formation of the gel monolith 402 in accordance with an embodimentof the present invention. In addition, using a base 410 comprisingremovably coupled components facilitates cleaning of the mold 410 andremoval of the gel monolith 402 from the mold 410.

[0105] In the embodiment schematically illustrated in FIG. 10, thecavity 413 is adapted to couple to the tubular projection 415 of thesecond base portion 416 when the second base portion 416 is coupled tothe mating surface 419. Similarly, the cavity 413 is adapted to coupleto the solid projection 417 of the third base portion 418 when the thirdbase portion 418 is coupled to the mating surface 419. The tubularprojection 415 is adapted to couple to the insert 430. In certain suchembodiments, the insert 430 fits through the cavity 413 and is coupledto the tubular projection 415 when the second base portion 416 iscoupled to the first base portion 414.

[0106] The solid projection 417 is adapted to fill the cavity 413 of thefirst base portion 414 once the insert 430 and second base portion 416are removed from the mold 400. In certain such embodiments, the solidprojection 417 has a top surface 411 which is hydrophobic and issubstantially flush with the first hydrophobic surface 412 when thethird base portion 418 is coupled to the first base portion 414.

[0107] In certain embodiments, the second hydrophobic surface 422 of thetubular outer wall 420 comprises PTFE, PMP, PS, or quartz coated withdichlorodimethylsilane (DCDMS). As described above in regard to the base410, the outer wall 420 can be fabricated entirely from PTFE, PMP, orPS, or can comprise other materials which have a hydrophobic coating onone or more surfaces, thereby providing the second hydrophobic surface422 in accordance with embodiments of the present invention. Inaddition, the second hydrophobic surface 422 in certain embodiments hasa good surface finish (i.e., it is polished and sufficientlydefect-free) to provide resultant glass surfaces which conform to thedesired specifications. In embodiments in which the outer wall 420accompanies the gel monolith 402 through additional processing steps,the outer wall 420 comprises materials which are able to withstand thevarious temperatures, pressures, and exposure to various corrosivecompounds to which the outer wall 420 is subjected during the formationof the gel monolith 402.

[0108] In certain embodiments, the second hydrophobic surface 422 iscylindrical and the outer wall 420 is removably coupled to the base 410.For example, as schematically illustrated in FIG. 10, the outer wall 420fits into a cylindrical recess 421 of the base 410 and can be removed tofacilitate cleaning of the various components of the mold 400 (e.g., thebase 410 and the outer wall 420) and to facilitate removal of theresultant gel monolith from the mold 400. In certain such embodiments,the cylindrical recess 421 of the base 410 comprises an o-ring (notshown) which couples to the outer wall 420, thereby forming aliquid-tight seal between the outer wall 420 and the base 410.

[0109] In certain embodiments, the outer hydrophobic surface 432 of theremovable tubular insert 430 comprises PTFE, PMP, PS, or quartz coatedwith dichlorodimethylsilane (DCDMS). As described above in regard to thebase 410 and the outer wall 420, the insert 430 can be fabricatedentirely from PTFE, PMP, or PS, or can comprise other materials whichhave a hydrophobic coating on one or more surfaces, thereby providingthe outer hydrophobic surface 432 in accordance with embodiments of thepresent invention. In addition, the outer hydrophobic surface 432 incertain embodiments has a good surface finish (i.e., it is polished andsufficiently defect-free) to provide resultant gel surfaces whichconform to the desired specifications.

[0110] In certain exemplary embodiments, the insert 430 comprises aHeraeus F300 quartz tube (available from Heraeus Tenevo, Inc. of Duluth,Ga.). In such embodiments, the outer hydrophobic surface 432 iscylindrical. In certain embodiments in which the mold 400 is used toform an optical fiber preform comprising a core portion and a claddingportion, the second hydrophobic surface 422 is cylindrical and the outerhydrophobic surface 432 is cylindrical and concentric with the secondhydrophobic surface 422. In such embodiments, the insert 430 is interiorto and spaced from the outer wall 420 so as to form a volume forreceiving a sol-gel solution.

[0111] In addition, the geometry of the core/cladding boundary of theresultant gel monolith is dependent on the geometry of the outerhydrophobic surface 432. For example, the smoothness, straightness, andovality of the resultant core/cladding boundary are dependent on thecorresponding parameters of the outer hydrophobic surface 432. Incertain embodiments, the outer hydrophobic surface 432 satisfies atolerance of ±1.5% of the diameter of the outer hydrophobic surface 432.In certain embodiments, the ratio of the diameter of the outerhydrophobic surface 432 of the insert 430 to the diameter of the secondhydrophobic surface 422 of the outer wall 420 is less than approximately½ and more preferably approximately equal to ⅓.

[0112] The insert 430 of certain embodiments is removably coupled to thebase 410 so as to form an airtight seal between the insert 430 and thebase 410. For example, as schematically illustrated in FIG. 10, theinsert 430 fits through the cavity 413 of the first base portion 414 tofit within the tubular projection 415 of the second base portion 416. Incertain such embodiments, the tubular projection 415 of the second baseportion 416 comprises an o-ring (not shown) which couples to the insert430, thereby forming a liquid-tight seal between the insert 430 and thesecond base portion 416.

[0113] In certain embodiments, the mold 400 further comprises a cap 440which is removably coupled to the outer wall 420 and the insert 430, asschematically illustrated in FIG. 10. While FIG. 10 illustrates the cap440 in conjunction with a particular embodiment of the mold 400, the cap440 is compatible with other embodiments, as described below. In theembodiment schematically illustrated in FIG. 10, the cap 440 comprises athird hydrophobic surface 442 and a hole 444 to which the insert 430 isremovably coupled. The cap 442 further comprises a cutout 446 thatprovides a conduit through which a sol-gel solution can be placed in themold 400 while the cap 440 is coupled to the outer wall 420. Inaddition, other configurations of the cap 440 are compatible withembodiments of the present invention.

[0114] The third hydrophobic surface 442 of the cap 440 comprises PTFE,PMP, or PS in certain embodiments. Similarly to the base 410, the cap440 can be fabricated entirely from PTFE, PMP, or PS, or can compriseother materials which have a hydrophobic coating on one or moresurfaces, thereby providing the third hydrophobic surface 442. Inembodiments in which the cap 440 accompanies the gel monolith 402through additional processing steps, the cap 440 comprises materialswhich are able to withstand the various temperatures, pressures, andexposure to various corrosive compounds to which the cap 440 issubjected during the formation of the gel monolith 402. The thirdhydrophobic surface 442 of the cap 440 reduces the probability of thecap 440 sticking to the gel monolith 402 or to other portions of themold 400, and helps to avoid impurities in the gel monolith 402. Incertain embodiments, the hole 444 is positioned so that the outerhydrophobic surface 432 is concentric with the second hydrophobicsurface 422.

[0115] As schematically illustrated in FIG. 11A, in certain embodiments,the mold 400 defines a first volume 450. The insert 430 is interior toand spaced from the outer wall 420 so as to form the first volume 450. Aportion of the first volume 450 is bounded by the first hydrophobicsurface 412, the second hydrophobic surface 422, and the outerhydrophobic surface 432. In certain embodiments, the first volume 450 isfurther defined by the third hydrophobic surface 442. The first volume450 is adapted to receive a first sol-gel solution 452, as schematicallyillustrated in FIG. 1B, which undergoes gelation to form the first gelportion 404.

[0116] In an exemplary embodiment, the first sol-gel solution 452 placedwithin the first volume 450 is allowed to gel in the first volume 450.As schematically illustrated in FIG. 11C, the resulting configurationhas at least a portion of the first volume 450 filled by the first gelportion 404, with the insert 430 defining a hole through the first gelportion 404.

[0117] In certain embodiments, after forming the first gel portion 404,the insert 430 is removed from the mold 400 in preparation of formingthe second gel portion 406, as schematically illustrated in FIG. 11C. Incertain such embodiments, removal of the insert 430 is performed slowlyand carefully to avoid damaging the first gel portion 404. In prior artsystems which use a solid rod to define a hole through a gel, the gelforms a substantially airtight seal with the rod, and removal of the rodgenerates a vacuum region in the volume vacated by the rod. Theatmospheric force on the rod due to this vacuum region hinders continuedremoval of the rod and can increase the likelihood of damaging the firstgel portion 404 during the removal of the rod.

[0118] Conversely, in embodiments of the present invention, the insert430 provides a conduit for gas to get to the volume vacated by theinsert 430 as it is pulled out of the first gel portion 404 and base410. In this way, embodiments of the present invention do not generatethe vacuum region and its corresponding atmospheric force whichotherwise hinders the removal of the insert 430.

[0119] As schematically illustrated in FIG. 11C, removal of the insert430 from the mold 400 and replacement of the second base portion 416with the third base portion 418 results in a configuration in which thefirst gel portion 404 has a substantially empty second volume 460extending through the first gel portion 404. In certain suchembodiments, the first gel portion 404 is a tubular gel monolith, andundergoes additional processing to form a sol-gel-derived tube, asdescribed more fully below. In other embodiments, the second volume 460is adapted to receive a second sol-gel solution 462 which undergoesgelation to form the second gel portion 406. In certain suchembodiments, a portion of the second volume 460 is bounded by the firstgel portion 404 and by the hydrophobic top surface 411 of the solidprojection 417 of the third base portion 418.

[0120] In an exemplary embodiment, the second sol-gel solution 462 isplaced within the second volume 460 and is allowed to gel in the secondvolume 460. As schematically illustrated in FIG. 11D, the resultingconfiguration has at least a portion of the second volume 460 filled bythe second gel portion 406. In embodiments in which the solid projection417 has a hydrophobic top surface 411 that is substantially flush withthe first hydrophobic surface 412, the corresponding ends of theresultant first gel portion 404 and second gel portion 406 aresubstantially flush with one another, thereby avoiding stress-generatingcorners in the interface region between the first gel portion 404 andthe second gel portion 406.

[0121] In certain embodiments, the first gel portion 404 and the secondgel portion 406 have different refractive indices and can be used in anoptical fiber preform. In certain such embodiments, the ratio of thediameter of the outer hydrophobic surface 432 to the second hydrophobicsurface 422 is approximately ⅓.

[0122] Embodiments of the process of multiple casting to form aresulting gel monolith 402 in accordance with embodiments of the presentinvention can have attributes which are particularly well-suited toforming optical fiber preforms and which have not been achieved by priorart systems. First, fabrication of optical preforms using multiplecastings can be less complicated than prior art processes which utilizegas deposition. Multiple casting is predominantly a solution-basedfabrication technique which can avoid the complexities and costsinherent in the gas-based chemistry of prior art deposition processes,such as gas handling, temperature control, and pollution control. Inaddition, optical preforms produced in accordance with embodiments ofthe present invention can be less expensive than those produced usingprior art processes, by avoiding the low material collectionefficiencies and the slow processing rates of deposition processes.

[0123] Second, by casting both the core portion and cladding portionusing sol-gel processes, embodiments of multiple casting do not requirelow-OH and low-transition-metal silica deposition tubes as do prior artprocesses. For example, in modified chemical vapor deposition (MCVD),silica material (which becomes the outer surface of the core portion ofthe fiber) is deposited within a deposition tube (which can become thecladding portion of the fiber) by introducing gases and vapors withinthe deposition tube while heating and rotating the deposition tube.Because the cladding portion interacts with the light transmittedthrough the fiber, the deposition tube must have high optical quality(e.g., low OH and impurity concentrations) to avoid attenuation of thetransmitted light.

[0124] Third, multiple casting in accordance with embodiments of thepresent invention can fabricate more compositionally complex opticalfiber preforms than can deposition processes. For example, multiplecastings of sol-gel materials can generate optical preforms comprisingorganic materials which would otherwise decompose under the hightemperatures inherent in deposition processes such as MCVD, outsidevapor deposition (OVD), or vapor axial deposition (VAD). In addition, byjudiciously selecting the sol-gel materials to use in the multiplecasting, embodiments of the present invention can generate tailoredrefractive index profiles across the optical fiber preform.

[0125] Fourth, multiple casting in accordance with embodiments of thepresent invention can be performed as batch processes (i.e., fabricatinga plurality of optical fiber preforms in parallel). And fifth, forming asleeve portion of a sol-gel-based optical fiber preform in accordancewith embodiments of the present invention, as described more fully below(e.g., rod-in-tube process), utilizes less sophisticated sleevingprocesses than do chemical-vapor-deposition processes.

[0126] In certain embodiments, as schematically illustrated in FIG. 10,the mold 400 further comprises a plug 470 which is removably coupled tothe insert 430. When coupled to the insert 430, the plug 470 forms anairtight seal between the plug 470 and the insert 430. As schematicallyillustrated in FIGS. 12A-12C, such embodiments can be used to form a gelmonolith 402 with interim steps in accordance with embodiments of thepresent invention.

[0127] In certain embodiments, the plug 470 comprises a material whichis chemically resistant to the corrosive compounds to which the plug 470may be exposed during processing. Examples of materials compatible withembodiments of the present invention include, but are not limited to,silicone, PTFE, PMP, PS, and fluoroelastomer such as Viton® availablefrom DuPont Dow Elastomers L.L.C. of Wilmington, Del. The material ofthe plug 470 can reduce the probability of the plug 470 sticking to theinsert 430 and helps to avoid impurities in the gel monolith 402.

[0128] The plug 470 is dimensioned to be removably fit onto the insert430 so as to form an airtight seal between the insert 430 and the plug470. In certain embodiments, the plug 470 is tapered so as to fit withinthe inner diameter of the insert 430 to form an airtight seal with theinner surface 431, as schematically illustrated in FIG. 10.

[0129] In certain embodiments, the mold 400 is assembled asschematically illustrated in FIG. 12A using the outer wall 420, thefirst base portion 414, and the second base portion 416. In certain suchembodiments, the first sol-gel solution 452 is placed within the volumebounded by the second hydrophobic surface 422, the first hydrophobicsurface 412, and the tubular projection 415 of the second base portion416. As schematically illustrated in FIG. 12B, the first sol-gelsolution 452 of the resulting configuration does not have a hole, andextends into the tubular projection 415 of the second base portion 416.

[0130] After placing the first sol-gel solution 452 in the mold 400, butbefore the first sol-gel solution 452 undergoes gelation, the insert 430is inserted through the hole 444 of the cap 440, into and through thefirst sol-gel solution 452, to couple to the tubular projection 415 ofthe second base portion 416. Embodiments in which the insert 430 isinserted into and through the first sol-gel solution 452 tend togenerate fewer bubbles in the first sol-gel solution 452 thanembodiments in which the first sol-gel solution 452 is poured into thevolume between the outer wall 420 and the insert 430. Reducing thenumber of bubbles formed in a sol-gel solution reduces the number ofpotential stress-generating defects in the resultant gel monolith,thereby lowering the probability of cracking of the gel monolith.

[0131] In embodiments in which the plug 470 is coupled to the insert430, as schematically illustrated in FIG. 12C, the insert 430 displacesthe first sol-gel solution 452 from the volume occupied by the insert430, including from the tubular projection 415 of the second baseportion 416. Due to the airtight seal between the plug 470 and theinsert 430, the volume inside the insert 430 remains substantially freeof the first sol-gel solution 452.

[0132] In such embodiments, the first sol-gel solution 452 is thenallowed to undergo gelation thereby forming the first gel portion 404.To remove the insert 430 from the mold 400 in preparation of forming thesecond gel portion 406, the plug 470 is removed from the insert 430,thereby breaking the airtight seal between the plug 470 and the insert430. In this way, a conduit for gas flow is provided through the insert430 so that gas is able to get to the volume vacated by the insert 430as the insert 430 is pulled out of the first gel portion 404 and base410. Such embodiments avoid the vacuum region and its correspondingatmospheric force which otherwise hinders the removal of the insert 430.Once the insert 430 is removed from the mold 400, the first gel portion404 can undergo further processing as described more fully below, or theprocess of forming the gel monolith 402 can continue as described abovein relation to FIGS. 11C-11D.

[0133] In certain embodiments, a small portion of the first sol-gelsolution 452 remains within the insert 430 and undergoes gelation. Theresulting gel within the insert 430 then blocks gas from flowing to thevolume vacated by the insert 430 as the insert 430 is removed from themold 400. In such embodiments, the gel within the insert 430 can bebroken up, thereby opening a conduit for gas to flow. For example, afterremoving the plug 470 from the insert 430, but before removing theinsert 430 from the mold 400, a probe can be extended into the insert430 to break apart any gel which has formed within the insert 430.

[0134]FIG. 13 schematically illustrates an exploded view of another mold500 for forming a gel monolith 502 comprising a first gel portion 504and a second gel portion 506 in accordance with embodiments of thepresent invention. FIGS. 14A-14E schematically illustrate interim stagesduring the formation of the gel monolith 502 using the mold 500 inaccordance with an embodiment of the present invention. The mold 500comprises a base 510 comprising a first hydrophobic surface 512. Themold 500 further comprises a tubular outer wall 520 comprising a secondhydrophobic surface 522 and the outer wall 520 is coupled to the base510. The mold 500 further comprises a removable tubular insert 530comprising an inner surface 531 and an outer hydrophobic surface 532.The mold 500 further comprises a removable cap 540 comprising a thirdhydrophobic surface 542 and a hole 544. The insert 530 is removablycoupled to the base 510 and the cap 540.

[0135] In the embodiment schematically illustrated in FIG. 13, the base510 comprises the first hydrophobic surface 512, a bottom surface 513,and a cavity 514 adapted to couple the base 510 with the insert 530. Thebase 510 is configured to fit within the outer wall 520, as describedmore fully below. In certain embodiments, the cavity 514 extends fromthe first hydrophobic surface 512 to the bottom surface 513 of the base510, while in other embodiments, the cavity 514 does not extend to thebottom surface 513.

[0136] In the embodiment schematically illustrated in FIG. 13, the mold500 further comprises a bottom wall 524 which encloses one end of theouter wall 520. The bottom wall 524 is adapted to couple with the base510 so that the base 510 is within a volume defined by the outer wall520 and the bottom wall 524, as illustrated in FIG. 14A. Using a base510 which is removably coupled to the bottom wall 524 facilitatescleaning of the mold components, as described herein.

[0137] Formation of the gel monolith 502 proceeds as described above inrelation to the embodiments of FIGS. 10-12. As schematically illustratedin FIG. 14A, in certain embodiments, the mold 500 defines a first volume550, a portion of which is bounded by the first hydrophobic surface 512,the second hydrophobic surface 522, and the outer hydrophobic surface532. The first volume 550 is adapted to receive a first sol-gel solution552 which undergoes gelation to form the first gel portion 504.

[0138] In an exemplary embodiment, the first sol-gel solution 552 isplaced within the first volume 550 and is allowed to gel in the firstvolume 550. As schematically illustrated in FIG. 14B, the resultingconfiguration has at least a portion of the first volume 550 filled bythe first gel portion 504, with the insert 530 defining a hole throughthe first gel portion 504.

[0139] In certain embodiments, after forming the first gel portion 504,the insert 530 is removed from the mold 500 in preparation of formingthe second gel portion 506, as schematically illustrated in FIG. 14C. Incertain such embodiments, the insert 530 provides a conduit for gas toget to the volume vacated by the insert 530 as it is pulled out of thefirst gel portion 504 and base 510. In this way, embodiments of thepresent invention do not generate the vacuum region and itscorresponding atmospheric force which otherwise hinders the removal ofthe insert 530.

[0140] As schematically illustrated in FIG. 14C, removal of the insert530 from the mold 500 results in a configuration in which the first gelportion 504 has a substantially empty second volume 560 extendingthrough the first gel portion 504. In such embodiments, a portion of thesecond volume 560 is bounded by the first gel portion 504. In certainembodiments, the first gel portion 504 is a tubular gel monolith, andundergoes additional processing to form a sol-gel-derived tube, asdescribed more fully below.

[0141] In an exemplary embodiment, the second sol-gel solution 562 isplaced within the second volume 560 and is allowed to gel in the secondvolume 560. As schematically illustrated in FIG. 14D, the resultingconfiguration has at least a portion of the second volume 560 filled bythe second gel portion 506. In certain such embodiments, as seen in FIG.14E, the edge between the cavity 514 and the first hydrophobic surface512 can have a sufficiently large radius of curvature to reducepotential stresses which would result from a sharp edge.

[0142] As described above in relation to the embodiments of FIGS. 11 and12, the embodiments schematically illustrated in FIGS. 13 and 14 arecompatible with use of a plug 570 which forms an airtight seal with theinner surface 531 of the insert 530. In such embodiments, the insert 530can be inserted into and through the first sol-gel solution 542 and intothe cavity 514 of the base 510.

[0143] In addition, in certain embodiments, the base 510 can be insertedinto the mold 500 after the first sol-gel solution 552 is placed in thevolume defined by the outer wall 520 and the bottom wall 524. In suchembodiments, the base 510 is inserted into and through the first sol-gelsolution 552 to couple to the bottom wall 524 in a manner that generatesfewer bubbles in the first sol-gel solution 552 than in embodiments inwhich the first sol-gel solution 552 is poured onto the base 510. Asdescribed above, reducing the number of bubbles formed in a sol-gelsolution reduces the number of potential stress-generating defects inthe resultant gel monolith, thereby lowering the probability of crackingof the gel monolith.

[0144]FIGS. 15A and 15B schematically illustrate alternativeconfigurations of the mold in accordance with embodiments of the presentinvention. In the embodiment illustrated in FIG. 15A, the mold 600comprises a base 610 comprising a first hydrophobic surface 612, amating surface 613 with a first seal 614, a cavity 615, a plug 616, arecess 617, and a removable second seal 618 between the cavity 615 andthe recess 617. The mold 600 further comprises an outer wall 620comprising a second hydrophobic surface 622, a tubular insert 630comprising an outer hydrophobic surface 632, and a cap 640 comprising athird hydrophobic surface 642 and a hole 644. The mating surface 613 isremovably coupled to the outer wall 620 and the first seal 614 forms aliquid-tight seal between the base 610 and the outer wall 620. Thecavity 615 is removably coupled to the insert 630. The second seal 618forms a removable liquid-tight seal between the cavity 615 and therecess 617. The plug 616 is removably coupled to the recess, wherebyremoving the plug 616 and the second seal 618 from the recess 617fluidly couples the cavity 615 and the recess 617.

[0145] In the embodiment schematically illustrated in FIG. 15A, thefirst hydrophobic surface 612 is flat and horizontal. In otherembodiments, the first hydrophobic surface 612 of the base 610 can betapered from the mating surface 613 of the base 610 towards the cavity615. In certain such embodiments, the tapered first hydrophobic surface612 is flat, while in other embodiments, it has a curvature, such asspherical. Tapered first hydrophobic surfaces 612 can serve tofacilitate removal of the gel monolith from the mold 600 and to reducepotential crack-inducing stresses within the gel monolith.

[0146] In addition, the first hydrophobic surface 612 of certainembodiments has a sufficiently large radius of curvature along the edgeof the cavity 615 so as to avoid stress-generating corners in theinterface region between the first gel and second gel portions. Thefirst hydrophobic surface 612, as well as any other surfaces of the mold600 which contact the gel monolith, has a good surface finish (i.e., itis polished and sufficiently defect-free) to provide resultant gelsurfaces which conform to the desired specifications.

[0147] In certain embodiments, the outer wall 620 is coupled to themating surface 613 of the base 610 via the first seal 614. In theembodiment illustrated in FIG. 15A, the first seal 614 is an o-ringwhich provides a liquid-tight seal between the base 610 and the outerwall 620. Other embodiments can utilize other configurations of thefirst seal 614 (e.g., an interference fit between the outer wall 620 andthe base 610). The first seal 614 is particularly useful to provide aliquid-tight seal in embodiments in which the base 610 and the outerwall 620 have different thermal expansion coefficients.

[0148] As illustrated in FIG. 15A, certain embodiments of the base 610comprise a plug 616 which fits into and couples to a recess 617 of thebase 610. In the embodiment schematically illustrated in FIG. 15A, theplug 616 and the base 610 are threaded with tapered NPT (National PipeThread) threads. Other embodiments can utilize other types of threads,or can utilize other methods of coupling the plug 616 and the base 610.Both the plug 616 and the recess 617 of certain embodiments can betapered to facilitate removably coupling the plug 616 within the recess617, as illustrated schematically in FIG. 15A.

[0149] The second seal 618 can provide a liquid-tight seal between thecavity 615 and the recess 617 of the base. In the embodiment illustratedin FIG. 15A, the second seal 618 is a compressible disk which iscompressed between the plug 616 and the recess 617 when the plug 616 isscrewed into the base 610. In such embodiments, the disk comprises amaterial which is more compressible than the materials of the plug 616or the recess 617 in the region where the disk is compressed. Otherembodiments can utilize other configurations or materials for the secondseal 618. The second seal 615 of certain embodiments is chemicallyresistant and has a hydrophobic surface which can contact the sol-gelsolution.

[0150] Upon removing the plug 616 and the second seal 618 from therecess 617, the cavity 615 and the recess 617 are fluidly coupled. Suchembodiments are particularly useful to provide a conduit for liquidremoval from the gel monolith during drying.

[0151] The insert 630 of certain embodiments is removably coupled to thebase 610, and as illustrated in FIG. 15A, fits snugly into the cavity615 of the base 610. In addition, certain embodiments of the second seal618 can also provide a liquid-tight seal between the insert 630 and thebase 610.

[0152] In the embodiment illustrated in FIG. 15B, the mold 700 comprisesa base 710 comprising a first hydrophobic surface 712, a bottom wall 713with a hole 714, and a plug 716. The mold 700 further comprises an outerwall 720 comprising a second hydrophobic surface 722, a tubular insert730 comprising an outer hydrophobic surface 732, and a cap 740comprising a third hydrophobic surface 742 and a hole 744.

[0153] The bottom wall 713 of the embodiment of FIG. 15B encloses oneend of the outer wall 720. The plug 716 is removably coupled to thebottom wall 713 via the hole 714, providing a removable liquid-tightseal between the plug 716 and the bottom wall 713. In certainembodiments, as schematically illustrated in FIG. 15B, the hole 714 andthe plug 716 are concentric with the second hydrophobic surface 722 anda portion of the plug 716 extends into the mold 700 past the firsthydrophobic surface 712. In such embodiments, the plug 716 couples tothe inner surface of the insert 730, thereby positioning the insert 730concentrically with the second hydrophobic surface 722. In certainembodiments, the coupling of the plug 716 with the insert 730 canprovide a removable liquid-tight seal between the plug 716 and theinsert 730, thereby keeping sol-gel solution from within the insert 730.

[0154] When the mold 700 is filled with sol-gel solution, the plug 716keeps the solution within the mold 700. Once the solution has gelled,the plug 716 can be removed to facilitate removal of liquid from thepores of the gel monolith during drying while the gel monolith remainsin the mold 700.

[0155]FIG. 16 is a flow diagram of a method 800 of forming a gelmonolith 402 having a first gel portion 404 and a second gel portion406. While the flow diagram of FIG. 16 illustrates a particularembodiment with steps in a particular order, other embodiments withdifferent orders of steps are also compatible with the presentinvention. In addition, while the description below refers to theexemplary embodiment schematically illustrated by FIGS. 11A-11D, variousother embodiments of the interim stages of the formation of the gelmonolith 402 are compatible with the present invention (e.g., theembodiments schematically illustrated by FIGS. 12A-12C, 14A-14D, and15A-15B).

[0156] In the embodiment diagrammed in FIG. 16, in an operational block810, a first sol-gel solution 452 is prepared with the first sol-gelsolution 452 comprising at least 3 mole % of a first catalyst. Asdescribed above, the first sol-gel solution 452 in certain embodimentsis prepared at a reduced mixing temperature, thereby increasing thegelation time of the first sol-gel solution 452 to facilitate subsequentfabrication steps. In certain embodiments, the first catalyst ishydrogen fluoride, while in other embodiments, the first catalystcomprises other compounds. The first sol-gel solution 452 comprisespreferably at least 3 mole % of the first catalyst, more preferably atleast 4 mole % of the first catalyst, and more preferably at least 10mole % of the first catalyst.

[0157] In an operational block 820, a mold 400 having a first volume 450and a second volume 460 is provided. At least a portion of the firstvolume 450 has a common boundary with at least a portion of the secondvolume 460. In certain embodiments, the second volume 460 is cylindricaland the first volume 450 is tubular and concentric with the secondvolume 460, as schematically illustrated in FIGS. 11A-11D.

[0158] In an operational block 830, the first gel portion 404 is formedin the first volume 450. Forming the first gel portion 404 comprisesallowing the first sol-gel solution 452 to gel in the first volume 450.In certain embodiments, as schematically illustrated in FIG. 11B, thefirst volume 450 is tubular, and confining the first sol-gel solution452 to the tubular first volume 450 results in a tubular first gelportion 404. As is described more fully below, in certain embodiments,the tubular first gel portion 404 can undergo further processing to forma sol-gel-derived tube.

[0159] In the embodiment schematically illustrated by FIG. 11B, thesecond volume 460 contains the removable insert 430 while forming thefirst gel portion 404 in the first volume 450. The removable insert 430can be placed in the second volume 460 before placing the first sol-gelsolution 452 in the first volume 450. Alternatively, the first sol-gelsolution 452 can be placed in both the first volume 450 and the secondvolume 460, and the removable insert 430 can then be inserted throughthe first sol-gel solution 452 prior to allowing the first sol-gelsolution 452 to gel in the first volume 450, thereby displacing thefirst sol-gel solution 452 out of the second volume 460.

[0160] In an operational block 840, a second sol-gel solution 462 isprepared with the second sol-gel solution 462 comprising at least 3 mole% of a second catalyst. As described above, the second sol-gel solution462 in certain embodiments is prepared at a reduced mixing temperature,thereby increasing the gelation time of the second sol-gel solution 462to facilitate subsequent fabrication steps. In certain embodiments, thesecond catalyst is hydrogen fluoride, while in other embodiments, thesecond catalyst comprises other compounds. In certain embodiments, thesecond catalyst is the same as the first catalyst. The second sol-gelsolution 462 comprises preferably at least 3 mole % of the secondcatalyst, more preferably at least 4 mole % of the second catalyst, andmore preferably at least 10 mole % of the second catalyst.

[0161] In an operational block 850, the second gel portion 406 is formedin the second volume 460 after the first sol-gel solution 452 has gelledalong the common boundary. Forming the second gel portion 406 comprisesallowing the second sol-gel solution 462 to gel in the second volume460. In the embodiment schematically illustrated by FIG. 11C, theremovable insert 430 is removed from the second volume 460 prior toforming the second gel portion 406 in the second volume 460. Asschematically illustrated in FIG. 11B, the second volume 460 of certainembodiments is cylindrical and the second gel portion 406 is formed byconfining the second sol-gel solution 462 to the cylindrical secondvolume 460 within the tubular first volume 450, and allowing the secondsol-gel solution 462 to gel.

[0162] In certain embodiments, the tubular first gel portion 404 isformed before forming the cylindrical second gel portion 406. A mold 400comprising a cylindrical outer wall 420 and a cylindrical removableinsert 430 concentric with the cylindrical outer wall 420 can beprovided in certain embodiments. In such embodiments, the first sol-gelsolution 452 can be placed in the tubular first volume 450 between theouter wall 420 and the insert 430. The insert 430 can then be removedafter allowing the first sol-gel solution 452 to gel, and the secondsol-gel solution 462 can be placed within the second volume 460 definedby the first gel portion 404.

[0163] Prior to placing the second sol-gel solution 462 within thesecond volume 460 defined by the first gel portion 404, in certainembodiments, a washing procedure is performed in which the second volume460 is filled with a dilute HF solution for a predetermined period oftime (typically 30 to 60 minutes), which is then removed. The dilute HFsolution can be diluted in water or in ethanol, with a typical HFconcentration of approximately 5 mole %. In this way, the commonboundary is washed prior to forming the second gel portion 406 in thesecond volume 460. This washing procedure can serve to enhance thebonding at the common boundary between the first gel portion 404 and thesecond gel portion 406 by removing residual (possibly hydrophobic)material left by the outer hydrophobic surface 432 of the insert 430 onthe inner surface of the first gel portion 404. In certain otherembodiments, a bonding agent (e.g., formamide) can be added to enhancethe bonding at the common boundary.

[0164] In certain embodiments, during the washing procedure, thetemperature of the first gel portion 404 is increased in preparation ofplacing the second sol-gel solution 462 within the second volume 460.The gelation of the second sol-gel solution 462 in the second volume 460can create heat in a short period of time, thereby potentially creatingthermal stresses across the first gel portion 404. Heating the first gelportion 404 (typically to approximately 40° C.) during the washingprocedure prior to the gelation of the second sol-gel solution 462 canreduce such thermal stresses.

[0165] In certain embodiments, the cylindrical second gel portion 406can be formed before forming the first tubular gel portion 404. In suchembodiments, a mold 400 comprising a cylindrical outer wall 420 and atubular removable insert 430 concentric with the cylindrical outer wall420 can be provided. In certain such embodiments, the inner surface ofthe insert 430 is hydrophobic and the second sol-gel solution 462 isplaced within the second volume 460 defined by the volume within thetubular removable insert 430. The insert 430 can then be removed afterallowing the second sol-gel solution 462 to gel, and the first sol-gelsolution 452 can be placed within the first volume 450 defined by thecylindrical second gel portion 406 and the outer wall 420 of the mold400.

[0166]FIG. 17 schematically illustrates a gel monolith 862 in accordancewith an embodiment of the present invention. The gel monolith 862comprises a cylindrical gel portion 864 and a tubular gel portion 866.The tubular gel portion 866 is around and concentric with thecylindrical gel portion 864. The gel monolith 862 is formed by a methodin accordance with the method diagrammed by FIG. 16, as described above.

[0167]FIG. 18 schematically illustrates a sol-gel-derived rod 872 inaccordance with an embodiment of the present invention. Thesol-gel-derived rod 872 comprises a cylindrical core portion 874 and atubular cladding portion 876 around and concentric with the core portion874. The sol-gel-derived rod 872 is formed by a process comprisingdrying a gel monolith 862 comprising a cylindrical gel portion 864 and atubular gel portion 866 around and concentric with the cylindrical gelportion 864. The gel monolith 862 is formed by a method in accordancewith the method diagrammed by FIG. 16, as described above. The processfor forming the sol-gel-derived rod 872 further comprises consolidatingthe gel monolith 862.

[0168] Drying the Gel Monolith

[0169] The embodiments disclosed herein form silica-based gel monolithswhich are virtually free of cracks. However, the methods and structuresdisclosed herein also have application to the formation of gel monolithsgenerally, including other oxide-based gel monoliths.

[0170] During gelation, the components of the sol undergo hydrolysis andpolymerization, resulting in a wet porous gel monolith 1000. Asschematically illustrated in FIG. 19, the gel monolith 1000 comprisespores 1002 filled with liquid 1004, an inner region 1006, and an outerregion 1008. During the drying of the gel monolith 1000, the gelmonolith 1000 shrinks in size, and capillary forces in the gel pores1002 arise as the amount of liquid 1004 in the gel monolith 1000 isreduced. If the drying of the gel monolith 1000 progresses too quicklyin one region of the gel monolith as compared to another region, theninhomogeneities in the capillary forces create stresses in the gelmonolith 1000, thereby causing cracks. If the drying of the gel monolith1000 progresses too slowly, then the fabrication process takes longerthan is economically desirable. In embodiments of the present invention,the drying rate of the gel monolith 1000 is controlled to avoid crackingand to provide economically rapid drying without generating largeinhomogeneities in the capillary forces during the drying of the gelmonolith 1000.

[0171] The wet porous gel monolith 1000 of certain embodiments isformed, as described above, by forming a liquid sol by mixing togetherorgano-metallic compounds, such as metal alkoxides, with solvents andcatalysts in predetermined proportions and at predeterminedtemperatures. Suitable metal alkoxide materials include, but are notlimited to, TEOS, TEOG, and TMOS. Solvents compatible with the presentinvention include, but are not limited to, ethanol and other alcohols,and suitable catalysts include, but are not limited to, HCl and HF.Alternatively, the liquid sol is prepared by mixing together inorganicmetal salts and water, which form a colloidal dispersion.

[0172] The formation of the wet porous gel monolith 1000 of certainembodiments also comprises stirring and pouring the liquid sol into amold. Colloidal silica-based particles are formed by hydrolysis andpolymerization reactions, with the colloidal particles linking together,thereby forming the wet porous silica gel monolith 1000 with pores 1002filled with liquid 1004.

[0173] The microstructure (e.g., pore diameter, surface area, volume,and distribution) of the resulting porous gel monolith 1000significantly affects the ability of the porous gel monolith 1000 towithstand the capillary forces during the drying process and the abilityto subsequently introduce desired dopants or additives to the porous gelmonolith 1000 to tailor its properties. For example, as described above,the tendency for cracking of gel monoliths may be reduced by tailoringthe gel microstructure so as to produce gel monoliths with larger porediameters. This microstructure is dependent in part on the relativeconcentrations of the solvents and the catalysts as described above, andcan be varied within a wide range by judicious selection of processparameters. In certain embodiments, drying control chemical additives(“DCCA”) are added to the sol to control its hydrolysis andpolymerization rates so as to tailor the pore diameters anddistributions.

[0174] The time required for formation of the wet porous gel monolith1000 is dependent on the sol composition, temperature, and the type ofcatalyst used. In certain embodiments, after formation of the wet porousgel monolith 1000, the pore liquid 1004 may be replaced by a secondliquid by removing the gel monolith 1000 from the mold and submerging itin the second liquid while at elevated temperatures (e.g., approximately60° C. to approximately 70° C.). After such a procedure, the liquid 1004within the pores 1002 of the gel monolith 1000 comprises primarily thesecond liquid. In certain embodiments, the second liquid comprisesprimarily ethanol, while in other embodiments, the second liquidcomprises other alcohols or water. Embodiments utilizing a second liquidcomprising an alcohol to replace the pore liquid 1004 comprising watercan help subsequent drying, because the diffusion rate of liquid throughthe pores can be increased and the capillary forces can be reduced.

[0175]FIG. 20 is a flow diagram of a method 1 100 of processing a gelmonolith 1000 in accordance with embodiments of the present invention.The gel monolith comprises pores 1002 filled with liquid 1004, an innerregion 1006, and an outer region 1008, an embodiment of which isschematically illustrated in FIG. 19. In certain embodiments, the method1100 results in a dried xerogel monolith, which is a gel monolith whichwas not dried under supercritical conditions. While the flow diagram ofFIG. 20 illustrates a particular embodiment with steps in a particularorder, other embodiments with different orders of steps are alsocompatible with the present invention.

[0176] In certain embodiments, the method 1100 is performed with the gelmonolith 1000 in a drying oven which allows the temperature applied tothe gel monolith 1000 to be controllably adjusted, resulting in atemporal temperature profile. Examples of heating technologies fordrying ovens compatible with embodiments of the present inventioninclude, but are not limited to, resistive heating, microwave heating,and infrared lamp heating.

[0177] In certain embodiments, the gel monolith 1000 is removed from themold prior to being placed in the drying oven, while in otherembodiments, the gel monolith 1000 and mold are placed in the dryingoven together. The gel monolith 1000 and mold can be inverted upon beingplaced in the drying oven in certain embodiments, to facilitate handlingof the gel monolith 1000 and removal of liquid 1004 from the pores 1002.

[0178] In the embodiment diagrammed in FIG. 20, in an operational block1120, a portion of the liquid 1004 is removed from the pores 1002 of thegel monolith 1000 while both the inner region 1006 and the outer region1008 of the gel monolith 1000 remain wet. In an operational block 1140,the volume of the gel monolith 1000 shrinks during the removing of theportion of the liquid 1004, with the gel monolith 1000 becomingcorrespondingly more dense. In an operational block 1160, substantiallyall of the remaining liquid 1004 is subsequently removed from the pores1002 of the gel monolith 1000. As is described more fully below,removing substantially all of the remaining liquid 1004 comprisesmodulating a temperature gradient between the outer region 1008 and theinner region 1006 of the gel monolith 1000.

[0179]FIG. 21 schematically illustrates a temporal temperature profilecompatible with embodiments of the present invention. FIG. 22 is a flowdiagram of an embodiment of the operational block 1120 in which aportion of the liquid 1004 is removed from the pores 1002 of the gelmonolith 1000. In an operational block 1122, the gel monolith 1000 isexposed to a temperature within a first temperature range. In anoperational block 1124, the temperature is increased from the firsttemperature range to a second temperature range substantially above theboiling temperature of the liquid 1004. In an operational block 1126,the temperature is maintained within the second temperature range for aperiod of time. In an operational block 1128, the temperature isdecreased from the second temperature range to a third temperature rangesubstantially below the second temperature range.

[0180] Exposing the wet porous gel monolith 1000 to elevatedtemperatures in the operational block 1120 increases the rate ofevaporation Θ_(evap) of liquid 1004 from the gel monolith 1000, andreduces the overall time required to dry the gel monolith 1000. Inaddition, the microstructure of the gel monolith 1000 is dependent onthe temporal temperature profile used to remove the liquid 1004 in theoperational block 1120. In certain embodiments, removal of the portionof the liquid 1004 in the operational block 1120 results in the gelmonolith 1000 having pores 1002 with a pore diameter distribution withan average pore diameter between approximately 200 and approximately1500 Angstroms, while in certain other embodiments, the average porediameter is between approximately 400 and approximately 1500 Angstroms,and in still other embodiments, the average pore diameter is betweenapproximately 1000 and approximately 1500 Angstroms.

[0181] In certain embodiments, such as that schematically illustrated inFIG. 21, the gel monolith 1000 is exposed to a temperature T₀ at time t₀in the operational block 1122. The temperature T₀ is in a firsttemperature range which in certain embodiments is between approximately0° C. and approximately 75° C., in other embodiments is betweenapproximately 0° C. and approximately 35° C., and in still otherembodiments is between approximately 18° C. and approximately 35° C. Incertain embodiments, as described above, the sol is prepared at areduced mixing temperature, and gelation of the sol also occurs at areduced temperature. In such embodiments, the first temperature rangecan be dependent on the temperature at which gelation of the gelmonolith 1000 occurs. However, in other embodiments, the gel monolith1000 is allowed to warm during or after gelation, and the drying of thegel monolith 1000 begins at a temperature T₀ which is approximately roomtemperature (e.g., approximately +18° C. to +35° C.).

[0182] In certain embodiments, the temperature is increased in theoperational block 1124 from T₀ to an elevated temperature T₁ at time t₁,as schematically illustrated in FIG. 21. The temperature T₁ is in asecond temperature range which in certain embodiments is belowapproximately 20° C. above the boiling temperature of the liquid 1004,in other embodiments is between approximately 3° C. and approximately15° C. above the boiling temperature of the liquid 1004, and in stillother embodiments is between approximately 5° C. and approximately 10°C. above the boiling temperature of the liquid 1004. In embodiments inwhich the liquid 1004 comprises primarily ethanol, the boilingtemperature of the liquid 1004 is approximately 78° C.

[0183] In certain embodiments, the temperature T₁ is selected based onthe overall compressive and tensile stresses on the gel monolith 1000.As T₁ increases, at some temperature, the overall tensile forces withinthe gel monolith 1000 will exceed the compressive forces, therebycracking the gel monolith 1000. Because ceramics maintain integrityunder compression, T₁ of certain embodiments is selected to keepcompressive forces on the gel monolith 1000 greater than tensile forces.

[0184] Increasing the temperature from the first temperature range tothe second temperature range in the operational block 1124 is performedin certain embodiments at a rate between approximately 0.01° C. andapproximately 10° C. per hour. Alternatively, in other embodiments,increasing the temperature is performed at a rate between approximately0.01° C. and approximately 1.5° C. per hour. In still other embodiments,increasing the temperature is performed at a rate approximately equal to0.042° C. per hour. While FIG. 21 shows the rate of temperature increasebetween times t₀ and t₁ to be generally linear, other embodimentscompatible with the present invention can use a nonlinear temperatureincrease, or can include interim decreases of the temperature.

[0185] In certain embodiments, as the temperature approaches the boilingtemperature of the liquid 1004, the temperature is increased at a slowerramp rate, thereby reducing the vapor pressure (i.e., tensile force)generated by the evaporating liquid 1004. After a period of time at theslower ramp rate, the ramp rate can be increased until a predeterminedtemperature is reached. In certain embodiments, this transition from theslower ramp rate to an increased ramp rate occurs at approximately 86.5°C. In certain other embodiments, this transition from the slower ramprate to an increased ramp rate occurs once a predetermined portion ofthe liquid 1004 is expelled from the pores 1002 and the gel monolith1000 approaches its final dimensions (i.e., once the tensile forces dueto vapor pressures have a reduced importance.

[0186] In the operational block 1126, the temperature of the gelmonolith 1000 is maintained within the second temperature range for aperiod of time. In certain embodiments, the period of time is betweenapproximately 1 hour and approximately 48 hours. In other embodiments,the period of time is between approximately 5 hours and approximately 15hours. In still other embodiments, the period of time is betweenapproximately 7 hours and approximately 10 hours. While FIG. 21 showsthe temperature to be generally constant during the time period (t₂-t₁)between times t₁ and t₂, other embodiments compatible with the presentinvention can vary the temperature T₁ during the period of time whilestaying in the second temperature range. As is described more fullybelow, various methods of monitoring the removal of the portion of theliquid 1004 from the gel monolith 1000 can be used in embodiments of thepresent invention to determine the period of time and when to initiateremoving substantially all of the remaining liquid 1004 in theoperational block 1160.

[0187] In certain embodiments, in the operational block 1128, thetemperature is decreased from the second temperature range to a thirdtemperature range substantially below the second temperature range at arate between approximately 1° C. and approximately 10° C. per hour. Inother embodiments, the temperature is decreased by stepping down the setpoint temperature of the oven approximately instantaneously from atemperature in the second temperature range to a lower temperature inthe third temperature range and allowing the gel monolith 1000 tore-equilibrize at the lower temperature.

[0188] In certain embodiments, the third temperature range is betweenapproximately 10° C. below and approximately 10° C. above the boilingtemperature of the liquid 1004. In other embodiments, the thirdtemperature range is between approximately 5° C. below and approximately5° C. above the boiling temperature of the liquid 1004. In still otherembodiments, the third temperature range is between approximately theboiling temperature of the liquid and approximately 2° C. above theboiling temperature of the liquid 1004. While FIG. 21 shows the rate oftemperature decrease between times t₂ and t₃ to be generally linear,other embodiments compatible with the present invention can use anonlinear temperature decrease, or can include interim increases of thetemperature.

[0189] In certain embodiments in which the gel monolith 1000 isgenerally cylindrical, the top and bottom portions of the gel monolith1000 have larger surface areas than do the sides of the gel monolith1000. Because the evaporation rate is proportional to the surface area,in such embodiments, the top and bottom portions can dry faster andhence shrink more than the sides of the gel monolith 1000. In certainsuch embodiments, the temperature can be reduced for a period of time sothat the liquid 1004 can diffuse to the drier top and bottom portions ofthe gel monolith 1000, thereby reducing the overall stresses on the gelmonolith 1000 by evening out the distribution of liquid 1004 throughoutthe gel monolith 1000.

[0190] Removing the liquid 1004 in the operational block 1120 results inthe shrinkage or decrease of the volume of the wet porous gel monolith1000 in the operational block 1140. The various parameters of thisremoval of the liquid 1004 (e.g., first temperature range, secondtemperature range, third temperature range, temperature increase rate,temperature decrease rate, and period of time in the second temperaturerange) are selected to provide a controlled drying rate of the gelmonolith 1000 in the operational block 1120 which is economically rapidbut avoids cracking.

[0191] The dimensional shrinking of the wet porous gel monolith 1000 inthe operational block 1140 is closely correlated with the amount ofliquid 1004 removed from the gel monolith 1000 in the operational block1120. In addition, since it is only the mass of a portion of the poreliquid 1004 which is removed, the mass of the gel monolith 1000 itselfremains substantially constant throughout the liquid removal of theoperational block 1120. Therefore, the density of the gel monolith 1000increases while the volume of the gel monolith 1000 shrinks during theremoval of the portion of the liquid 1004.

[0192] The dimensional or linear gel shrinkage provides a measure of theincreasing density of the gel monolith 1000 in the operational block1140. For example, a linear gel shrinkage of a dimension of 10% (i.e.,the dimension is 90% of its original size) corresponds to an increase inthe density of the gel monolith 1000 of approximately 37%. In theembodiment illustrated in FIG. 21, beginning from a linear gel shrinkagedefined to be 0% at time t₀, the gel monolith 1000 shrinks by someamount during the period of increasing temperature between times t₀ andt₁. The shrinkage of the wet porous gel monolith 1000 then continues asthe gel monolith 1000 is held at the temperature T₁ in the secondtemperature range for a period of time (t₂-t₁) between t₁ and t₂. Duringthe period of time (t₂-t₁) between t₂ and t₃, additional shrinkage ofthe wet porous gel monolith 1000 can occur, as schematically illustratedin FIG. 21.

[0193] As liquid 1004 is removed from the pores 1002 of the gel monolith1000, the gel monolith 1000 shrinks in size yet remains wet, until thedensity of the gel monolith 1000 reaches its critical gel densityρ_(crit), past which there is little or no shrinkage due to removal ofliquid 1004. Further removal of liquid 1004 from regions of the gelmonolith 1000 which have reached the critical gel density ρ_(crit)results in the drying of those regions. The actual critical gel densityρ_(crit) for a particular gel monolith 1000 is a function of variousfactors, including, but not limited to its chemical composition,catalysts, and the temporal temperature profile used during the removalof liquid 1004. In certain embodiments, as illustrated in FIG. 21, thecritical gel density ρ_(crit) corresponds to a gel monolith linearshrinkage of approximately 24%, which corresponds to a pure silica gelmonolith 1000. In other embodiments in which the gel monolith 1000 isGe-doped, the critical gel density ρ_(crit) can correspond to a gelmonolith linear shrinkage of approximately 30%.

[0194] In the embodiment schematically illustrated in FIG. 21, thetemperature is reduced between times t₂ and t₃, until reaching T₂ in thethird temperature range. In certain embodiments, this reduction of thetemperature in the operational block 1128 is performed when the gelmonolith 1000 has reached a selected gel density which is close to, butless than the critical gel density ρ_(crit). The selected gel densitycorresponding to time t₂, for the embodiment illustrated in FIG. 21, isapproximately 22%. The selected gel density for a particular gelmonolith 1000 is a function of various factors including, but notlimited to, its chemical composition, catalysts, geometry (e.g., surfacearea to volume ratio), and the temporal temperature profile used toremove the portion of the liquid 1004 in the operational block 1120.

[0195] Besides triggering the decrease of the temperature of theoperational block 1128, the selected gel density in certain embodimentsis used to initiate the operational block 1160 in which substantiallyall of the remaining liquid 1004 is removed from the pores 1002 of thegel monolith 1000. In embodiments in which the selected gel density isless than the critical gel density ρ_(crit), subsequently removingsubstantially all of the remaining liquid 1004 from the pores 1002 ofthe gel monolith 1000 is initiated before the wet porous gel monolith1000 has densified to substantially its critical gel density ρ_(crit).

[0196] In certain embodiments, subsequently removing substantially allof the remaining liquid 1004 from the pores 1002 of the gel monolith1000 is initiated when the linear shrinkage of the gel monolith 1000 isbetween approximately 15% and approximately 35%. In certain otherembodiments, subsequently removing substantially all of the remainingliquid 1004 from the pores 1002 of the gel monolith 1000 is initiatedwhen the linear shrinkage of the gel monolith 1000 is betweenapproximately 20% and approximately 30%. In still other embodiments,subsequently removing substantially all of the remaining liquid 1004from the pores 1002 of the gel monolith 1000 is initiated when thelinear shrinkage of the gel monolith 1000 is between approximately 22%and approximately 27%.

[0197] In alternative embodiments, rather than measuring the gel densityby continually monitoring the linear shrinkage of the gel monolith 1000to detect the selected gel density, the weight of the portion of theliquid 1004 removed from the pores 1002 of the gel monolith 1000 ismonitored. In such embodiments, the amount of liquid 1004 removed fromthe gel monolith 1000 is used to initiate subsequently removingsubstantially all of the remaining liquid 1004 from the pores 1002 ofthe gel monolith 1000.

[0198] In certain embodiments, the weight of the removed liquid 1004 ismonitored by collecting the evaporated liquid 1004 from the oven,re-condensing the liquid 1004, and weighing the resultant condensate.The evaporated liquid 1004 can be collected via a piping system whichprovides a conduit for heated vapor from the oven to reach a containeron a weight scale. Since the atmosphere in the oven is saturated withvapor from the liquid 1004, upon entering the piping system and thecontainer, the vapor cools, re-condenses, and flows into the containerto be weighed. In certain embodiments, the piping system and thecontainer are at approximately room temperature, while in otherembodiments, a cooling system (e.g., a condensing unit) is used to coolthe piping system and the container to a temperature below roomtemperature.

[0199] After first empirically determining the weight of the collectedcondensate corresponding to the selected gel density for a gel monolith1000 of a particular geometry and composition, the weight of thecollected condensate provides a measure of the amount of liquid removedfrom the gel monolith 1000 and the resultant gel density. Expressed as apercentage of the weight of the initial wet porous gel monolith 1000, incertain embodiments, the weight of the removed liquid 1004 whichinitiates removing substantially all of the remaining liquid 1004 isbetween approximately 40% and 65%. In other embodiments, the weight ofthe removed liquid 1004 which initiates removing substantially all ofthe remaining liquid 1004 is between approximately 40% and 50%. In stillother embodiments, the weight of the removed liquid 1004 which initiatesremoving substantially all of the remaining liquid 1004 is betweenapproximately 44% and 50%.

[0200] In addition to monitoring the linear shrinkage of the gelmonolith 1000 or the condensate weight, in certain other embodiments,visual examination of the gel monolith 1000 can be used to initiatesubsequently removing substantially all of the remaining liquid 1004from the pores 1002 of the gel monolith 1000. In such embodiments, thewet porous gel monolith 1000 has a clear, slightly bluish appearancefrom the time to at which the temperature begins to be increased, to thetime at which the gel monolith 1000 reaches its critical gel densityρ_(crit). This appearance of the gel monolith 1000 is indicative of ahomogeneous gel monolith 1000 with pore diameters in the range ofapproximately 200 Angstroms to approximately 1500 Angstroms.

[0201] In certain such embodiments, a visual imaging system can be usedto monitor the visual appearance of the gel monolith 1000. For example,a digital camera and a microprocessor can determine the height of thegel monolith 1000 to within approximately 1 mm, and can monitor the gelmonolith 1000 for the formation of white, opaque features larger thanapproximately 1 mm. The visual imaging system can be coupled to thecontrol system of the oven so that the temperature of the gel monolith1000 is controlled in response to its size and visual appearance. Othervisual imaging systems are compatible with embodiments of the presentinvention.

[0202] Continual exposure to temperatures in the second temperaturerange after reaching the critical gel density ρ_(crit) of the gelmonolith 1000 causes the outer region 1008 of the gel monolith 1000 todry out more quickly than the inner region 1006, resulting in largerpore diameters near the surface of the gel monolith 1000 as compared tothose in the inner region 1006 of the gel monolith 1000. Thisinhomogeneity of pore diameters can be evident by white, opaque featuresappearing at the surface of the gel monolith 1000, while the center ofthe gel monolith 1000 can remain relatively clear. In certainembodiments, the outer region 1008 is dried before the inner region1006, and liquid 1004 from the inner region 1006 diffuses to the outerregion 1008. In such embodiments, white, opaque features can be observedto form just inside the surface of the gel monolith 1000, with the innerregion 1006 remaining transparent. As the outer region 1008 is driedfurther, more of the surface becomes white and opaque, with the innerregion 1006 remaining transparent.

[0203]FIG. 23 is a flow diagram of an embodiment of the operationalblock 1160 in which substantially all of the remaining liquid 1004 isremoved from the pores 1002 of the gel monolith 1000 in accordance withembodiments of the present invention. In an operational block 1162, theouter region 1008 of the gel monolith 1000 is exposed to a temperaturewithin a fourth temperature range. In an operational block 1164, atemperature gradient between the outer region 1008 and the inner region1006 is modulated. As is described more fully below, in certainembodiments, the outer region 1008 of the gel monolith 1000 is exposedto a temperature within the fourth temperature range until the gelmonolith 1000 is substantially dried, with interim periods in which theouter region 1008 is exposed to higher temperatures in a fifthtemperature range, thereby modulating a temperature gradient between theinner region 1006 and the outer region 1008. In certain embodiments,modulation of the temperature gradient comprises varying the magnitudeof the temperature gradient, while in other embodiments, modulationfurther comprises varying the sign or direction of the temperaturegradient relative to the inner region 1006 and the outer region 1008.

[0204] In certain embodiments, during the removal of substantially allof the remaining liquid 1004 in the operational block 1160, the gelmonolith 1000 shrinks slightly (until the critical gel density ρ_(crit)is reached), and the liquid content of the gel monolith 1000 is reduced,thereby drying the gel monolith 1000. The fourth temperature range ofthe operational block 1162 is selected in certain embodiments to providea rate of drying which minimizes inhomogeneities in the capillary forcesand the overall stresses on the gel monolith 1000, thereby avoidingcracking of the gel monolith 1000. In certain such embodiments, thefourth temperature range corresponds to a rate of evaporation Θ_(evap)from the outer region 1008 that is substantially equal to or less thanthe rate of diffusion Θ_(diff) of liquid 1004 through the pores 1002 ofthe gel monolith 1000. Under such conditions, the liquid 1004 whichevaporates from the surface of the gel monolith 1000 is replaced byliquid 1004 from the inner region 1006 of the gel monolith 1000. The gelmonolith 1000 of such embodiments dries primarily by diffusion, with theliquid 1004 from the inner region 1006 diffusing to the outer region1008.

[0205] In certain embodiments, the fourth temperature range is betweenapproximately 10° C. below and approximately 10° C. above the boilingtemperature of the liquid 1004. In certain other embodiments, the fourthtemperature range is between approximately 5° C. below and approximately5° C. above the boiling temperature of the liquid 1004. In still otherembodiments, the fourth temperature range is between approximately theboiling temperature of the liquid 1004 and approximately 2° C. above theboiling temperature of the liquid 1004. In the embodiment illustrated inFIG. 21, the temperature T₂ at time t₃ is within both the thirdtemperature range and the fourth temperature range, thereby providingcontinuity between the operational block 1128 and the operational block1162. Other embodiments compatible with the present invention can use afourth temperature range that does not overlap with the thirdtemperature range.

[0206] While FIG. 21 shows the temperature in the fourth temperaturerange to be generally constant, other embodiments compatible with thepresent invention can vary the temperature while staying in the fourthtemperature range. In certain embodiments, the temperature is increasedwithin the fourth temperature range at a rate between approximately 0.3and 20 days per degree Celsius, while in other embodiments, thetemperature increase rate is between approximately 1 and approximately10 days per degree Celsius, and in still other embodiments, thetemperature increase rate is between approximately 2 and approximately 5days per degree Celsius. During such slowly-varying increases of thetemperature, the inner region 1006 of the gel monolith 1000 remains atapproximately the same temperature as is the outer region 1008 of thegel monolith 1000. Therefore, such slowly-increasing temperatures do notgenerate a substantial temperature gradient between the inner region1006 and the outer region 1008 of the gel monolith 1000.

[0207] In certain embodiments, a temperature gradient between the outerregion 1008 and the inner region 1006 is modulated in an operationalblock 1164 by exposing the outer region 1008 to a temperature within thefourth temperature range and exposing the outer region 1008 to atemperature within a fifth temperature range higher than the fourthtemperature range. By exposing the outer region 1008 of the gel monolith1000 to temperatures in the fifth temperature range while the innerregion 1006 is effectively at a temperature within the fourthtemperature range, a temperature gradient is generated between the innerregion 1006 and the outer region 1008. Similarly, once the inner region1006 is effectively at an elevated temperature above the fourthtemperature range, by exposing the outer region 1008 to a temperature inthe fourth temperature range, a temperature gradient is again generatedbetween the inner region 1006 and the outer region 1008. As used herein,a temperature gradient in which the outer region 1008 is at a highertemperature than is the inner region 1006 is described as a positivetemperature gradient, and a temperature gradient in which the outerregion 1008 is at a lower temperature than is the inner region 1006 isdescribed as a negative temperature gradient.

[0208] In the embodiment illustrated in FIG. 21, the rate of temperatureincrease or decrease between the fourth temperature range and the fifthtemperature range is rapid enough to generate the temperature gradientbetween the inner region 1006 and the outer region 1008 of the gelmonolith 1000. In certain embodiments, the temperature is increased ordecreased approximately instantaneously by stepping the set pointtemperature of the oven between a temperature in the fourth temperaturerange and a temperature in the fifth temperature range and allowing thegel monolith 1000 to heat up or cool down in accordance with themodified temperature. In certain embodiments, the absolute value of therate of temperature change is between approximately 60° C./hour andapproximately 155° C./hour. In other embodiments, the absolute value ofthe rate of temperature change is approximately equal to 135° C./hour.Other embodiments can utilize nonlinear temperature changes between thefourth temperature range and the fifth temperature range. In certainembodiments, the absolute value of the temperature increase from thefourth to the fifth temperature range can be different from the absolutevalue of the temperature decrease from the fifth to the fourthtemperature range.

[0209] In certain embodiments, the fifth temperature range is less thanapproximately 180° C. In other embodiments, the fifth temperature rangeis between approximately 100° C. and approximately 150° C. In stillother embodiments, the fifth temperature range is between approximately120° C. and approximately 130° C. In certain embodiments, the fifthtemperature range corresponds to an evaporation rate Θ_(evap) of theliquid 1004 from the outer region 1008 which is greater than or equal toa diffusion rate Θ_(diff) of the liquid 1004 in the pores 1002 of thegel monolith 1000. Under such conditions, the outer region 1008 driesfaster than does the inner region 1006 since liquid 1004 is removed fromthe outer region 1008 via evaporation faster than liquid 1004 isreplaced by diffusion from the inner region 1006 to the outer region1008. One result of such conditions is that the outer region 1008becomes opaque before the inner region 1006 becomes opaque.

[0210] In the exemplary embodiment schematically illustrated in FIG. 21,the outer region 1008 is exposed to a temperature within the fourthtemperature range for a period of time (t₄-t₃) between times t₃ and t₄.In certain such embodiments, the time period (t₄-t₃) between times t₃and t₄ is sufficiently long so that at time t₄, the temperature of theinner region 1006 and the temperature of the outer region 1008 are bothwithin the fourth temperature range. As described above, in certainembodiments the temperature applied to the outer region 1008 during thetime period (t₄-t₃) between times t₃ and t₄ is constant or is varyingsufficiently slowly so that the inner region 1006 remains atapproximately the same temperature as is the outer region 1008. In suchembodiments, there is not a substantial temperature gradient between theinner region 1006 and the outer region 1008 during the time period(t₄-t₃).

[0211] In embodiments in which the fourth temperature range correspondsto a rate of evaporation Θ_(evp) from the outer region 1008 that issubstantially equal to or less than the rate of diffusion Θ_(diff) ofliquid 1004 through the pores 1002, the liquid 1004 evaporating from thesurface of the gel monolith 1000 is replaced by liquid 1004 from theinner region 1006 of the gel monolith 1000. In such embodiments, theouter region 1008 does not dry faster than does the inner region 1006during the time period (t₄-t₃) between times t₃ and t₄.

[0212] At time t₄ in the exemplary embodiment of FIG. 21, the outerregion 1008 is exposed to a temperature within the fifth temperaturerange, thereby generating a positive temperature gradient between theouter region 1008 and the cooler inner region 1006. This positivetemperature gradient will exist for some time while the temperaturewithin the fifth temperature range is applied, but the positivetemperature gradient will decrease in magnitude as the inner region 1006warms, eventually reaching zero once the inner region 1006 is at thesame temperature as the outer region 1008 (i.e., once the inner region1006 and outer region 1008 are equilibrated).

[0213] Because the rate of evaporation Θ_(evap) is proportional totemperature, the rate of evaporation Θ_(evap) from the outer region 1008will be faster in the fifth temperature range than in the fourthtemperature range. In embodiments in which the fifth temperature rangecorresponds to an evaporation rate Θ_(evap) which is greater than orequal to the diffusion rate Θ_(diff) for temperatures in the fourthtemperature range, while the positive temperature gradient exists,liquid 1004 is removed from the outer region 1008 via evaporation fasterthan liquid 1004 is replaced by diffusion from the inner region 1006.During such times, the outer region 1008 dries faster than does theinner region 1006. In addition, the heat applied to the outer region1008 is absorbed by the evaporating liquid 1004, thereby contributing tothe temperature gradient between the outer region 1008 and the innerregion 1006 by inhibiting the applied heat from diffusing to and warmingthe inner region 1006.

[0214] In the exemplary embodiment of FIG. 21, the outer region 1008 isexposed to a temperature in the fifth temperature range for a period oftime (t₅-t₄) between t₄ and t₅. In certain embodiments, the outer region1008 is exposed to a temperature in the fifth temperature range for aperiod of time between approximately 30 minutes and approximately 5hours. In other embodiments, the outer region 1008 is exposed to atemperature in the fifth temperature range for a period of time betweenapproximately one hour and approximately 2 hours. In still otherembodiments, the outer region 1008 is exposed to a temperature in thefifth temperature range for a period of time between approximately 1.5hours and approximately 2 hours.

[0215] In certain embodiments, the period of time (t₅-t₄) between t₄ andt₅ is selected to allow most, if not all, of the outer region 1008 tobecome opaque white before lowering the temperature. Such embodimentshave a drier outer region 1008 and a wetter inner region 1006. Once thetemperature is lowered, the liquid 1004 from various portions of thewetter inner region 1006 can diffuse into various portions of the drierouter region 1008 at approximately equal rates, thereby avoidingstresses in the gel monolith 1000.

[0216] The period of time during which the outer region 1008 is exposedto a temperature in the fifth temperature range can be described byexamining the forces on the gel monolith 1000 in certain embodiments.While the positive temperature gradient exists between the outer region1008 and the inner region 1006, there are two main forces acting on thegel monolith 1000: vapor pressure (tensile force) and capillary force(compressive force). While in the fifth temperature range, the outerregion 1008 will have a net tensile force because the vapor pressuredominates over the capillary forces at these temperatures. Similarly,while in the fourth temperature range, the inner region 1006 will have anet compressive force because the capillary forces dominate at thesetemperatures. Gel monoliths 1000 comprising ceramics or oxide-basedmaterials are more stable under compression than under tension.Therefore, certain such embodiments avoid cracking of the gel monolith1000 by maintaining tensile forces which do not exceed compressiveforces. The roles of compression and tension forces in gel monoliths isdiscussed further by Brinker & Scherer in “Sol-Gel Science, The Physicsand Chemistry of Sol-Gel Processing,” pages 483-498, Academic Press,1990, which is incorporated in its entirety by reference herein.

[0217] This condition of keeping tensile forces less than compressiveforces can constrain the period of time during which the outer region1008 is exposed to the fifth temperature range in certain embodiments.After a sufficiently long period of time, the entire gel monolith 1000,including the inner region 1006, will be at a temperature within thefifth temperature range. Under such conditions, there is no longer atemperature gradient between the outer region 1008 and the inner region1006, and the vapor pressure dominates over the capillary forces acrossthe gel monolith 1000. Thus, the gel monolith 1000 will be under tensionand can crack. Therefore, in accordance with embodiments of the presentinvention, the outer region 1008 is exposed to a temperature within thefifth temperature range only for relatively short periods of time so asto avoid conditions for cracking.

[0218] At time t₅ in the exemplary embodiment of FIG. 21, the outerregion 1008 is exposed to a temperature within the fourth temperaturerange, thereby cooling the outer region 1008. In embodiments in whichthe outer region 1008 becomes cooler than the inner region 1006, anegative temperature gradient is generated between the outer region 1008and the warmer inner region 1006. This negative temperature gradientwill exist for some time while the temperature within the fourthtemperature range is applied, but the negative temperature gradient willdecrease in magnitude as the inner region 1006 cools, eventuallyreaching zero once the inner region 1006 is at the same temperature asthe outer region 1008.

[0219] In embodiments in which the outer region 1008 does not reachtemperatures below that of the inner region 1006, cooling the outerregion 1008 reduces the magnitude of the positive temperature gradientand hastens the equalization of temperatures between the outer region1008 and the inner region 1006. Whether the outer region 1008 reachestemperatures below that of the inner region 1006 is dependent on detailsof the temporal temperature profile, such as the temperatures appliedand the periods of time that the temperatures were applied.

[0220] By allowing the outer region 1008 to cool, the rate ofevaporation Θ_(evap) is reduced and the temperature gradient graduallydecreases in magnitude, eventually reaching zero. Once both the innerregion 1006 and outer region 1008 are again at temperatures within thefourth temperature range, the gel monolith 1000 dries primarily bydiffusion and the overall stresses on the gel monolith 1000 areminimized. As described above, the liquid 1004 from the inner region1006 diffuses to the drier, outer region 1008.

[0221] FIGS. 24A-C schematically illustrate other temporal temperatureprofiles in accordance with embodiments of the present invention. Incertain embodiments, modulating the temperature gradient between theinner region 1006 and the outer region 1008 further comprises cyclingthe temperature through a plurality of cycles. Each cycle comprisesexposing the outer region 1008 to the fourth temperature range for afirst time period, increasing the temperature from the fourthtemperature range to the fifth temperature range, and exposing the outerregion to the fifth temperature range for a second time period. Thetemperature is increased between the fourth temperature range and thefifth temperature range at a rate to generate a substantial temperaturegradient between the outer region and the inner region.

[0222] In certain embodiments, each cycle has substantially the sameparameters as do the other cycles. For example, the temporal temperatureprofile illustrated in FIG. 24A comprises three cycles. Each cycleexposes the outer region 1008 to a temperature T₂ within the fourthtemperature range for a first time period Δt₁ and exposes the outerregion 1008 to a temperature T₃ within the fifth temperature range for asecond time period Δt₂. In addition, the rates of temperature increaseand decrease for each cycle are substantially the same, and aresufficiently rapid to generate substantial temperature gradients betweenthe outer region and the inner region, as described above.

[0223] While the embodiment illustrated in FIG. 24A comprises threecycles, other embodiments compatible with the present invention comprisetwo, four, or more cycles. In addition, other temporal temperatureprofiles in accordance with embodiments of the present invention cancomprise cycles with differing first time periods, second time periods,temperatures, or rates of temperature increase or decrease. For example,FIG. 24B illustrates an embodiment comprising two cycles with differingtemperatures, and FIG. 24C illustrates an embodiment comprising threecycles with differing first time periods and differing second timeperiods.

[0224] In certain embodiments, the first time period is betweenapproximately one hour and approximately 30 hours. In certain otherembodiments, the first time period is between approximately 5 hours andapproximately 20 hours.

[0225] In certain embodiments, the second time period is betweenapproximately 10 minutes and approximately 15 hours. In certain otherembodiments, the second time period is between approximately 10 minutesand approximately 10 hours. In still other embodiments, the second timeperiod is between approximately 1.5 hours and approximately 2 hours.

[0226] In certain embodiments, as schematically illustrated in FIGS. 21and 24A-C, the temporal temperature profile also comprises a relativelybrief exposure of the gel monolith 1000 to high temperatures once thegel monolith 1000 is dried (i.e., the liquid 1004 has been completelydriven from the pores 1002 of the gel monolith 1000). This period ofheightened temperatures is used to drive the remaining vapor from thepores 1002 of the gel monolith 1000. In certain such embodiments, thetemperature is ramped up to approximately 180° C. over a period ofapproximately 18 hours, and is held at this heightened temperature forapproximately 3 hours to approximately 10 hours. In addition, tofacilitate the removal of vapor from the pores 1002 of the gel monolith1000, certain embodiments comprises backfilling the drying oven with aninert gas, nitrogen, air, or a combination thereof, at atmosphericpressure during this exposure to high temperatures.

[0227]FIG. 25 schematically illustrates an exemplary temporaltemperature profile which was applied to a gel monolith 1000 inaccordance with embodiments of the present invention. The gel monolith1000 was formed from a sol-gel solution comprising a formulation with amole ratio of TEOS:Ge:ethanol:HF:water of 1:0.105:2.5:0.25:2.2. At timet₀, removing a portion of the liquid 1004 from the pores 1002 of the gelmonolith 1000 began by placing the wet porous gel monolith 1000 in thedrying oven and exposing the gel monolith 1000 to a temperature ofapproximately 23° C., which is within the first temperature range ofcertain embodiments. The temperature in the drying oven was thenincreased linearly, eventually reaching a temperature of approximately72° C. after approximately 40 hours. For the next approximately 194hours, the outer region 1008 was exposed to a temperature whichincreased generally linearly from approximately 72° C. to approximately87° C., which is within the second temperature range of certainembodiments. During this period of increasing temperature, thetemperature increased from the first temperature range to the secondtemperature range which is substantially above the boiling temperatureof the liquid 1004 (approximately 78° C. for ethanol) and thetemperature was maintained within the second temperature range for aperiod of time (while still increasing).

[0228] Approximately 235 hours after placing the gel monolith 1000 inthe drying oven, the temperature was reduced from approximately 87° C.to approximately 80° C., which is within the third temperature range ofcertain embodiments. During the removal of the portion of the liquid1004, the volume of the gel monolith 1000 shrank, with the gel monolith1000 becoming correspondingly more dense.

[0229] Once the temperature reached approximately 80° C., removal ofsubstantially all of the remaining liquid 1004 from the pores 1002 ofthe gel monolith 1000 began. For approximately 6 hours, the outer region1008 was exposed to a temperature of approximately 80° C., which iswithin the fourth temperature range of certain embodiments, and atemperature gradient between the outer region 1008 and the inner region1006 was then modulated by cycling the temperature through a pluralityof cycles.

[0230] Modulating the temperature gradient began with a firsttemperature cycle comprising the approximately 6-hour exposure of theouter region 1008 to approximately 80° C., which is within the fourthtemperature range of certain embodiments. The first temperature cyclefurther comprised increasing the temperature from the fourth temperaturerange to a temperature of approximately 125° C., which is within thefifth temperature range of certain embodiments. The first temperaturecycle further comprised exposing the outer region 1008 to the fifthtemperature range for approximately 2.5 hours.

[0231] Modulating the temperature gradient continued with two additionaltemperature cycles. Each of these cycles comprises exposing the outerregion 1008 to approximately 80° C. for approximately 20 hours,increasing the temperature to approximately 125° C., and exposing theouter region 1008 to this temperature for approximately 2.5 hours. Thetemperature was then reduced and maintained at approximately 80° C. forapproximately 28 hours. The temporal temperature profile also comprisesa relatively brief exposure of the gel monolith 1000 to hightemperatures once the gel monolith 1000 was dried to drive the remainingvapor from the pores 1002. The oven was backfilled with nitrogen gas andthe temperature was ramped up to approximately 180° C. over a period ofapproximately 17 hours, and was held at approximately 180° C. forapproximately 10 hours. The temperature was then reduced back toapproximately room temperature (approximately 23° C.) under the nitrogengas atmosphere.

[0232]FIG. 26 graphically illustrates the resultant pore diameterdistributions for five different solution formulations after drying inaccordance with embodiments of the present invention. Table 1 providesinformation regarding these five solution formulations and the resultantpore diameter distributions. In addition to the listed formulation, eachof the solutions of FIG. 26 and Table 1 have a formulation with a moleratio of TEOS:ethanol:water of 1:2:2. TABLE 1 % of Pores % of Pores PoreAverage Within ± Mode Within ± Pore Surface Pore 10%, Pore 10%,Formulation Volume Area Diameter ±30%, ±45% Diameter ±30%, ±45% Monolith(mole ratio) (cc/g) (m²/g) (Å) of Average (Å) of Mode A HF 0.12 1.167518.1 90.1 35% 78 70% 85% 95% 100% 100% B HF 0.16 1.812 244.2 296.9 5%198 65% 80% 95% 100% 100% C HF 0.25 3.67 292.4 501.4 15% 374 15% Ge0.105 45% 40% 100% 90% D HF 0.34 3.32 180.8 735 20% 587 50% 65% 95% 100%100% E HF 0.4 2.66 95.74 1114 20% 809 30% 60% 90% 100% 100%

[0233] Each of the xerogel monoliths of FIG. 26 and Table 1 was preparedin accordance with embodiments of the present invention as describedherein. In certain embodiments, a sol comprising metal alkoxide and acatalyst at a catalyst concentration is first formed. The sol is thengelled to form a wet gel monolith, which is dried and shrunk by exposingthe wet gel monolith to a temporal temperature profile, thereby forminga xerogel monolith. The catalyst, the catalyst concentration, and thetemporal temperature profile for such embodiments are controlled andpreselected to obtain the xerogel monolith having certain physicalproperties.

[0234] The pore diameter distributions of FIG. 26 and Table 1 weremeasured using either an Autosorb-6B or Autosorb-3B surface area andpore size analyzer manufactured by Quantachrome Corporation of BoyntonBeach, Fla. As described above, and as seen in FIG. 26 and Table 1, themean pore diameters of xerogel monoliths fabricated in accordance withembodiments of the present invention correlate generally with theconcentration of the catalyst HF in the solution.

[0235] In certain embodiments, the resultant xerogel monolith has a porediameter distribution with an average pore diameter betweenapproximately 200 Å and approximately 1500 Å. In certain suchembodiments, the average pore diameter is between approximately 400 Åand approximately 1500 Å, while in certain other embodiments, the meanpore diameter is between approximately 1000 Å and approximately 1500 Å.Similarly, in certain embodiments, the resultant xerogel monolith has apore diameter distribution with a mode pore diameter betweenapproximately 200 Å and approximately 1500 Å.

[0236] In certain embodiments, at least 20% of the pores of theresultant xerogel monolith have diameters within approximately ±10% ofthe average pore diameter. In certain other embodiments, at least 45% ofthe pores of the resultant xerogel monolith have diameters withinapproximately ±30% of the average pore diameter. In certain embodiments,at least 30% of the pores have diameters within approximately ±10% ofthe mode pore diameter, while in certain other embodiments, at least 90%of the pores have diameters within approximately ±30% of the mode porediameter.

[0237] Consolidating the Gel Monolith

[0238] Once dried, the gel monolith is densified into an optical-qualityglass monolith by a consolidating process (i.e., sintering). The glassphase is characterized by an amorphous structure. Alternatively, inother embodiments, the densification can result in a monolith which hasa crystalline structure. The consolidating process can result in furtherlinear shrinkage of the monolith, eventually reaching approximately 60%(i.e., to 40% of the starting size of the wet gel monolith).

[0239] Consolidation is performed by placing the dry gel monolith in afurnace and exposing it to a consolidating temporal temperature profilein an atmosphere comprising various gases. Numerous consolidatingtemporal temperature profiles and atmospheres are compatible withembodiments of the present invention, including those described byKirkbir, et al., in U.S. Pat. No. 5,254,508, which is incorporated inits entirety by reference herein. As described by Kirkbir, et al., theconsolidating temporal temperature profile and atmospheres can be chosento fabricate optical fiber preforms which undergo reduced bubbling ofthe germanium-doped core portion during the high-temperature fiberdrawing process.

[0240]FIG. 27 is a flowchart of a consolidating process 1200, inaccordance with embodiments of the present invention, performed on amonolith in a furnace. In an operational block 1210, the monolith isexposed to an atmosphere comprising oxygen and nitrogen and heatedslowly from room temperature to a temperature of no more than 1000° C.The operational block 1210 of certain embodiments can compriseintermittent periods at which the temperature is held constant. Forexample, in certain embodiments, the operational block 1210 comprisesmaintaining the temperature at approximately 160° C. for two hours, atapproximately 240° C. for 20 hours, raising the temperature toapproximately 700° C. in 30 hours, and holding at this temperature for39 hours. In addition, the monolith can also be exposed to intermittentvacuum treatments during the operational block 1210. These intermittentvacuum treatments, in which the monolith is exposed to pressures of lessthan approximately atmospheric pressure for periods of time betweenapproximately 10 minutes and approximately 10 hours, can serve toshorten the overall time the monolith is exposed to the conditions ofthe operational block 1210. In certain embodiments, the monolith isexposed to absolute pressures of approximately 0.7 psi (i.e.,approximately −14 psi relative to atmospheric pressure) during theoperational block 1210.

[0241] The processing step of the operational block 1210 can removeunwanted molecules from the pore surfaces of the monolith. In certainembodiments, these unwanted molecules can include, but are not limitedto, organic species, corrosive effluent molecules such as HF, andbyproducts of the hydrolysis and polymerization reactions, such asalcohol, H₂O, or hydrocarbons. In embodiments having a Ge-dopedmonolith, this processing step can also remove GeF₂, GeF₄, or GeCl₄ fromthe pore surfaces of the monolith.

[0242] In certain embodiments, the consolidating process 1200 furthercomprises an operational block 1220 in which the monolith is exposed toa halogen-containing gas treatment while at a temperature betweenapproximately 600° C. and approximately 1100° C. This processing stepcan remove hydroxyl groups (OH) from the pore surfaces of the monolithwhich would otherwise degrade the optical performance of the resultantglass. In addition, this processing step can remove unwanted free GeOmolecules from a Ge-doped monolith.

[0243] In certain embodiments of the operational block 1220, themonolith is exposed to a gas comprising an inert gas (such as helium ornitrogen), and at least 0.1% of a halogen-containing gas such aschlorine gas (Cl₂). In certain embodiments, the gas further comprisesoxygen. In still other embodiments, the gas comprises approximately 10%by volume of Cl₂ and approximately 90% by volume of O₂. Otherhalogen-containing gases compatible with embodiments of the presentinvention include, but are not limited to, SiF₄, NF₃, SF₆, HF, SOCl₂,CCl₄, and SiCl₄. The temperature during the operational block 1220 ofcertain embodiments can be held constant, or can be varied with apredetermined temporal temperature profile. For example, in certainembodiments, the operational block 1220 comprises holding thetemperature at approximately 700° C. for 5 hours, increasing toapproximately 800° C. in 10 hours, holding at approximately 800° C. for5 hours, increasing to approximately 900° C. in 10 hours, and holding atthis temperature for 10 hours. As described above in relation to theoperational block 1210, the operational block 1220 of certainembodiments can comprise one or more intermittent vacuum treatmentswhich can shorten the overall time the monolith is exposed to theconditions of the operational block 1220.

[0244] In certain embodiments, the consolidating process 1200 furthercomprises an operational block 1230 in which the monolith is exposed toan oxygen-containing gas treatment while at a temperature less thanapproximately 1150° C. This processing step can remove chlorine from themonolith and burn off residual carbon atoms. In certain embodiments, theoxygen-containing gas comprises at least 10% oxygen (O₂), with thebalance comprising helium or nitrogen or both. The temperature duringthe operational block 1230 of certain embodiments can be held constant,or can be varied with a predetermine temporal temperature profile. Forexample, in certain embodiments, the operational block 1230 comprisesmaintaining the temperature at 900° C. for 29 hours, increasing to 1020°C. in 10 hours, and increasing to 1040° C. in 20 hours. As describedabove, the operational block 1230 of certain embodiments can compriseone or more intermittent vacuum treatments which can shorten the overalltime the monolith is exposed to the conditions of the operational block1230.

[0245] In certain embodiments, the consolidating process 1200 furthercomprises an operational block 1240 in which the monolith is exposed toa helium gas purge treatment which can remove oxygen gas from the poresof the monolith. In addition, for Ge-doped monoliths, embodiments of theoperational block 1240 can remove unwanted free GeO₂ molecules from themonolith. In certain embodiments, this processing step lasts at least 30minutes during a temperature less than approximately 1150° C. Asdescribed above, the operational block 1240 of certain embodiments cancomprise one or more intermittent vacuum treatments which can shortenthe overall time the monolith is exposed to the conditions of theoperational block 1240.

[0246] In certain embodiments, the consolidating process 1200 furthercomprises an operational block 1250 in which the monolith is heated to atemperature of at least 1150° C. for at least 5 minutes. This processingstep can densify and consolidate the monolith into optical qualityglass. In certain embodiments, the temperature is increased from thetemperature of the operational block 1240 at a rate of at leastapproximately 10° C. per hour. For example, in certain embodiments, theoperational block 1250 comprises increasing the temperature toapproximately 1160° C. in 12 hours, increasing to approximately 1280° C.in 15 hours, maintaining at approximately 1280° C. for 10 hours, anddecreasing to approximately 1120° C. in 2 hours. In certain embodiments,this processing step is performed in vacuum, while in other embodiments,it is performed in an atmosphere of helium gas to facilitate heattransfer during consolidation.

[0247] In certain embodiments, the consolidating process 1200 furthercomprises an operational block 1260 in which the monolith is cooled downto room temperature in a nitrogen or helium gas environment. In certainembodiments, the operational block 1260 comprises cooling toapproximately 1120° C. in 6 hours, cooling to approximately 850° C. in26 hours, cooling to approximately 500° C. in 18 hours, and coolingfreely to approximately 20° C. Other embodiments can utilize othertemporal temperature profiles which avoid stresses which would otherwiseresult in poor optical quality of the monolith.

[0248] Below are described particular examples of consolidatingtemperature profiles and the atmospheres in accordance with embodimentsof the present invention:

EXAMPLE 1

[0249] For 27 hours, a dry gel monolith was heated from room temperature(approximately 20° C.) to 400° C. in an atmosphere of 20% oxygen and 80%nitrogen. The monolith was then heated to 700° C. in 45 hours in anatmosphere of 40% oxygen and 60% nitrogen. The monolith was then heatedto 800° C. in 5 hours, then to 900° C. in 10 hours, and held at thistemperature for 10 hours in an atmosphere of 10% chlorine and 90%helium. The monolith was then held at 900° C. for 95 hours in anatmosphere of 80% oxygen and 20% helium. The monolith was then heated to1000° C. in 15 hours in an atmosphere of 10% oxygen and 90% helium, andheld at 1000° C. for 8.5 hours in pure helium. The monolith was thenheated in an atmosphere of helium to a temperature of 1280° C. in onehour and held at that temperature for 8 minutes. The monolith was thenallowed to cool to room temperature over the course of 24 hours in anitrogen atmosphere. The resultant monolith was consolidated into anoptical quality glass sol-gel-derived rod.

EXAMPLE 2

[0250] For 18 hours, a dry Ge-doped gel monolith was heated from roomtemperature to 160° C. and then to 400° C. in an atmosphere of 20%oxygen and 80% nitrogen. The monolith was then heated to 700° C. in 25hours and held at that temperature for 20 hours in an atmosphere of 40%oxygen and 60% nitrogen. In an atmosphere of 10% chlorine and 90%helium, the monolith was heated to 800° C. in 10 hours. The monolith wasthen heated to 900° C. in 10 hours, and held at 900° C. for 5 hours inan atmosphere of 6% chlorine and 94% oxygen. The monolith was thenheated to 950° C. in 10 hours and held at 950° C. for 25 hours in anatmosphere of 80% oxygen and 20% helium. The monolith was then heated inan atmosphere of helium at a temperature of 950° C. for 10 hours andthen heated to 1100° C. in 5 hours and further heated to a temperatureof 1280° C. in one hour and held at that temperature for 10 minutes.After cooling to room temperature in helium, the resultant monolith wasconsolidated into an optical quality glass sol-gel-derived rod.

[0251] Forming the Optical Fiber Preform

[0252] An optical fiber preform, from which optical fiber is drawn,typically consists of a doped silica cylindrical core portion and atleast one tubular cladding portion around and concentric with the coreportion. Optical fibers with sufficient optical properties (e.g., lowattenuation) typically have a refractive index of the cladding portionwhich is between approximately 0.3% and approximately 0.4% less than therefractive index of the core portion. To increase the refractive indexof the core portion, the core portion can be doped with germanium,phosphorous, or a combination of Ge and P. Both Ge and P have deepultraviolet and infrared cutoff wavelengths. To decrease the refractiveindex of the cladding portion, the cladding portion can be doped withfluorine.

[0253] Various methods are described in the prior art which utilizevapor deposition of fine particles (or soot) of pure silica,fluorine-doped silica, and germanium-doped silica for producing opticalfiber preforms with the desired refractive indices. For example, outsidevapor deposition (OVD) is used by Corning, Inc. of Corning, N.Y. tofabricate its SMF-28 optical fibers. As schematically illustrated inFIG. 28A, the OVD process utilizes a burner 1310 (supplied byappropriate vapors and fuel) which moves laterally along a horizontal,rotating mandrel 1320, depositing germanium-doped silica layer-by-layeronto the mandrel to a predetermined thickness (which eventually becomesthe core portion). After depositing a pure silica cladding portion inthe same manner onto the germanium-doped core portion, the mandrel 1310is removed, and the remaining tube is consolidated (or densified) atapproximately 1500° C. to 1600° C. to form the optical fiber preform.

[0254] Another vapor deposition technique described in the prior art forforming optical fiber preforms is called vertical axial deposition(VAD), and is schematically illustrated in FIG. 28B. During the VADprocess, the core portion and the cladding portion are deposited axiallyand simultaneously using multiple burners. The first burner 1330deposited the core portion and subsequent burners 1332, 1334 deposit thecladding portion over the core portion as the boule is rotated and drawnupwards. The VAD process can provide continuous preform formation, withdeposition rates suitable for batch processes. After deposition, thedeposited soot is consolidated to form the optical fiber preform undersimilar conditions as in OVD.

[0255] Another common vapor deposition technique described in the priorart for forming optical fiber preforms is called modified chemical vapordeposition (MCVD), and is schematically illustrated in FIG. 28C. Duringthe MCVD process, a traversing oxygen/hydrogen burner 1340 is used toheat a rotating pure silica tube 1350. High-purity gas mixtures areinjected into one end of the tube 1350, producing soot 1360 which isdeposited and vitrified on the inside diameter of the tube. In certainconfigurations, a cladding portion is deposited first, which compriseseither pure silica or fluorine-doped silica. In certain otherconfigurations, the cladding portion corresponds to the pure silica tube1350 itself. The core portion, comprising germanium-doped silica, isdeposited next, until the tube 1350 is closed by the deposited soot1360. After deposition, the deposited soot 1360 is consolidated to formthe optical fiber preform.

[0256] Once formed, the optical fiber preform 1370 is used to fabricatea continuous strand of optical fiber. The completed optical fiberpreform 1370 is drawn using a draw tower 1400, as schematicallyillustrated in FIG. 28D. A movable preform holder 1410 holds the preform1370 which extends into the furnace 1420. The tip of the preform 1370 isheated until a piece of molten glass begins to fall, pulling a thinglass strand or fiber 1430 behind it. The fiber 1430 is threaded throughthe other components of the draw tower 1400, including acomputer-controlled tractor assembly 1440 which continues to pull thefiber 1430 through the draw tower 1400, and a take-up spool 1450 whichcollects the resultant fiber 1430.

[0257] The diameter of the fiber 1430 is dependent on the speed at whichthe fiber 1430 is pulled through the draw tower 1400, and the diameteris monitored by a precise detector 1460 coupled to the tractor assembly1440. To ensure a specified outside diameter of the fiber 1430, thepulling speed of the tractor assembly 1400 is modified in response tosignals from the detector 1460. Coatings can be applied to the fiber1430 using an applicator 1470, and the coatings can be cured usingultraviolet lamps 1480.

[0258] Alternatively, the optical fiber preform, including the coreportion and cladding portion, can be fabricated using sol-geltechniques. However, prior art systems which utilize sol-gel techniquessuffer from various difficulties which have hindered the mass productionof sol-gel-derived optical fiber preformis. As described by Kirkbir, etal., these difficulties include precipitation of germanium, therebyreducing the homogeneity of the resultant gel monolith, and bubbling ofgermanium-doped glass rods during the high-temperature fiber drawingprocess. In addition, prior art techniques result in gel monoliths withrelatively small pore sizes, thereby making it more difficult to dry andconsolidate the gel monolith without cracking.

[0259] As described herein, sol-gel-derived rods fabricated inaccordance with embodiments of the present invention avoid problemsencountered when using prior art sol-gel techniques. In certainembodiments, filtering the sol-gel solution after mixing with a 0.05 μmfilter removes Ge precipitates. In other embodiments, the sol-gelsolution comprises phosphorous which stabilizes Ge in the network, andfacilitates achieving the desired refractive index while using less Ge.In other embodiments, consolidation under an oxygen-containingatmosphere can serve to stabilize Ge in the network. As described above,the xerogel monolith is consolidated so as to reduce or eliminatebubbling of the glass rods during the drawing process. In addition, thepore diameter distributions for wet gel monoliths and xerogel monolithsfabricated in accordance with embodiments of the present invention aresufficiently large to facilitate drying and consolidating withoutcracking the resultant monolith.

[0260]FIG. 29 is a flow diagram of a method 1500 of forming an opticalfiber preform 1600 in accordance with certain embodiments of the presentinvention. FIGS. 30A-30E schematically illustrate various interim stagesin the fabrication of the optical fiber preform 1600 in accordance withembodiments of the present invention. While the flow diagram of FIG. 29illustrates a particular embodiment with steps in a particular order,other embodiments with different orders of steps are also compatiblewith the present invention.

[0261] In the embodiment described by FIG. 29, the method 1500 comprisesan operational block 1510 in which a sol-gel-derived rod 1610 having afirst diameter D, is formed. As illustrated in the flow diagram of FIG.29, forming the sol-gel-derived rod 1610 comprises an operational block1512 in which a sol-gel solution comprising at least 3 mole % of acatalyst is prepared. As described above, preparing such a sol-gelsolution in certain embodiments is performed at a mixing temperaturesubstantially below room temperature, thereby allowing higher catalystconcentrations with sufficiently long gelation times.

[0262] In an operational block 1514, the sol-gel solution is allowed toundergo gelation to form a wet gel monolith, as described above. Incertain embodiments, the sol-gel solution is placed in a cylindricalmold in which the sol-gel solution undergoes gelation, resulting in acylindrical wet gel monolith. As described herein, in certain otherembodiments, the sol-gel solution is placed in a tubular mold in whichthe sol-gel solution undergoes gelation, resulting in a tubular wet gelmonolith. The cross-section of such tubular wet gel monoliths can besquare, rectangular, hexagonal, or have an arbitrary shape. In stillother embodiments, the sol-gel solution can be one of a plurality ofsol-gel solutions for multiple castings, resulting in a multiply-castwet gel monolith. The sol-gel-derived rod 1610 formed by suchembodiments can comprise a step-index or gradient-index glass, in whichportions of the sol-gel-derived rod 1610 with differing refractiveindices are formed by separate castings.

[0263] In an operational block 1516, the wet gel monolith is dried andshrunk by exposing the wet gel monolith to a temporal temperatureprofile. As described above, drying and shrinking the wet gel monolithforms a xerogel monolith. In an operational block 1518, the xerogelmonolith is consolidated as described above, thereby forming thesol-gel-derived rod 1610.

[0264] In the embodiment described by FIG. 29, the method 1500 furthercomprises an operational block 1520 in which the sol-gel-derived rod1610 is drawn to substantially reduce its diameter. In this way, a drawnrod 1620 is formed, the drawn rod 1620 having a second diameter D₂ lessthan the first diameter D₁. FIG. 30A schematically illustrates the drawnrod 1620 in relation to the sol-gel-derived rod 1610.

[0265] Drawing the sol-gel-derived rod 1610 in certain embodimentscomprises heating the sol-gel-derived rod 1610 at a softeningtemperature (which can be at least 1400° C.) in a furnace tower,extracting one end of the sol-gel-derived rod 1610 from the furnacetower at an extraction speed, and adjusting the extraction speed to formthe drawn rod 1620 with the second diameter D₂ substantially equal to apredetermined value. Certain embodiments of the drawing process aresimilar to the prior art process of drawing an optical fiber preform tofabricate optical fiber, as described above. In certain embodiments, thefirst diameter D₁ is between approximately 30 mm and approximately 65mm, and the second diameter D₂ is between approximately 4 mm andapproximately 8 mm.

[0266] In certain embodiments, as illustrated in the flow diagrams ofFIGS. 31A and 31B, the method 1500 further comprises an operationalblock 1530 in which a substrate portion 1632 is formed around the drawnrod 1620, thereby forming a substrate rod 1630 with a third diameter D₃.The substrate portion 1632 of certain embodiments corresponds to asubstrate portion of the resultant fiber, while the sol-gel-derived rod1610 corresponds to the core portion of the resultant fiber.

[0267] In certain embodiments, as illustrated in FIGS. 30B and 31A,forming the substrate portion 1632 comprises fusing a substrate tube1634 onto the drawn rod 1620. In certain such embodiments, fusing thesubstrate tube 1634 onto the drawn rod 1620 can comprise inserting thedrawn rod 1620 into the substrate tube 1634, heating the substrate tube1634, collapsing the substrate tube 1634 onto the drawn rod 1620, andannealing the substrate tube 1634 and the drawn rod 1620. A vacuum canbe applied in a region between the substrate tube 1634 and the drawn rod1620. In addition, in certain embodiments, a gas can be introduced inthe region between the substrate tube 1634 and the drawn rod 1620.Fusing silica tubes onto silica rods is a known process, and personsskilled in the art can select process parameters (e.g., heating andannealing temperatures, vacuum pressure, gas concentrations, andcollapse rates) in accordance with embodiments of the present invention.

[0268] In an exemplary embodiment, a sol-gel-derived Ge-doped rod 1610is reduced to a drawn rod 1620 having a predetermined second diameterD₂, as illustrated in FIG. 30A, and cut to a predetermined length (e.g.,1000 to 1500 mm). The predetermined second diameter D₂ is calculatedbased on the size of the preform to be manufactured and on the type ofoptical fiber being fabricated (e.g., single-mode or multimode fiber).Quartz handles can be welded onto the ends of the sol-gel-derived rod1610, as well as on the silica substrate tube 1634 and silica sleevingtube 1644, to facilitate handling and to minimize waste of material.

[0269] During the drawing process on the draw tower 1400, asschematically illustrated in FIG. 28D, the sol-gel-derived rod 1610 isheated using an induction furnace 1420 and the diameter of the drawn rod1620 is measured online using a detector 1460 comprising a diametergauge coupled to the tractor assembly 1440 via the control system (notshown) so that the speed of the draw is maintained at a desired level toyield the predetermined second diameter within tolerances. The drawn rod1620 is inspected and firepolished, if necessary, to remove surfacebubbles or other imperfections.

[0270] Continuing the exemplary embodiment, a substrate tube 1634 (e.g.,Heraeus F300) is selected based on the size of the preform to bemanufactured. A cleaning pass is performed on the inside surface of thesubstrate tube 1634 by one torch pass in an atmosphere comprisingapproximately 0.3% Cl₂, approximately 80% O₂, with the balance He. Afteretching approximately 100 μm thickness from the drawn rod 1620, thedrawn rod 1620 is inserted into the substrate tube 1634 on a sleevinglathe, which is typically in either a vertical or horizontalconfiguration. The substrate tube 1634 is positioned to be concentricwith the drawn rod 1620, with a gap of approximately 2 mm between theinside diameter of the substrate tube 1634 and the outside diameter ofthe drawn rod 1620.

[0271] After an additional cleaning pass comprising a torch pass in anatmosphere comprising approximately 0.3% Cl₂, approximately 80% O₂, withthe balance He, a helium soak is performed for approximately 3 hours bytraversing the torch along the substrate tube 1634 in an atmospherecomprising approximately 17% He and approximately 83% O₂. The substratetube 1634 is then collapsed onto the drawn rod 1620 to form thesubstrate rod 1630 by heating in an atmosphere of approximately 17% Heand approximately 83% O₂ at a vacuum of approximately 0.15 inches ofwater (0.28 Torr) between the drawn rod 1620 and the substrate tube1634. The oxygen is turned off just prior to the collapse of thesubstrate tube 1634 to reduce the probability of bubble formation.Forming the substrate rod 1630 further comprises stretching thecollapsed substrate tube 1634 and drawn rod 1620 to have a predetermineddiameter. A sleeve tube 1644 can then be collapsed onto the substraterod 1630 using similar processes to fabricate the optical fiber preform1600 to final predetermined dimensions.

[0272] In addition, forming the substrate portion 1632 can furthercomprise applying a deposition layer onto an inner surface of thesubstrate tube 1634 prior to fusing the substrate tube 1634 onto thedrawn rod 1620 and consolidating the deposition layer. Such embodimentscan utilize known MCVD techniques to apply the deposition layer, whichcan have a different refractive index than does the drawn rod 1620, butmatched to the substrate tube 1634. In this way, the refractive index ofthe resultant optical fiber preform 1600 can be tailored to apredetermined profile.

[0273] In certain other such embodiments, forming the substrate portion1632, as illustrated in FIGS. 30C and 31B, comprises applying adeposition layer onto the drawn rod 1620 and consolidating thedeposition layer. Such embodiments can utilize known OVD techniques toapply the deposition layer. In such embodiments, the silica material canbe deposited onto a doubly-cast sol-gel-derived monolith, not directlyonto a surface of a Ge-doped silica rod, prior to drawing the rod.

[0274] In certain embodiments, as illustrated in the flow diagrams ofFIGS. 32A and 32B, the method 1500 further comprises an operationalblock 1540 in which a sleeve portion 1642 is formed around the substraterod 1630, thereby forming the optical fiber preform 1640 with a fourthdiameter D₄. The sleeve portion 1642 of certain embodiments serves toprovide a fourth diameter D₄ which conforms to a predetermined valueconducive to subsequent processing. In certain such embodiments, asillustrated in FIGS. 30D and 32A, forming the sleeve portion 1642comprises fusing a sleeve tube 1644 onto the substrate rod 1630. Incertain embodiments, the sleeve tube 1644 comprises a Heraeus F300quartz tube, and the fusing process is as described above in relation tofusing the substrate tube 1634 onto the drawn rod 1620.

[0275] In certain such embodiments, fusing the sleeve tube 1644 onto thesubstrate rod 1630 can comprise inserting the substrate rod 1630 intothe sleeve tube 1644, heating the sleeve tube 1644, collapsing thesleeve tube 1644 onto the substrate rod 1630, and annealing the sleevetube 1644 and the substrate rod 1630. A vacuum can be applied in aregion between the sleeve tube 1644 and the substrate rod 1630. Inaddition, in certain embodiments, a gas can be introduced in the regionbetween the sleeve tube 1644 and the substrate rod 1630. The sleeve tube1644 of certain embodiments comprises substantially defect-free (i.e.,low bubble density) silica glass. Sleeve tubes 1644 compatible withembodiments of the present invention can be obtained from HeraeusTenevo, Inc. of Duluth, Ga. or GE Quartz, Inc. of Willoughby, Ohio. Asdescribed above, fusing silica tubes onto silica rods is a knownprocess, and persons skilled in the art can select process parameters(e.g., heating and annealing temperatures, vacuum pressure, gasconcentrations, and collapse rates) in accordance with embodiments ofthe present invention.

[0276] In certain other such embodiments, forming the sleeve portion1642, as illustrated in FIGS. 30E and 32B, comprises applying adeposition layer onto the substrate rod 1630 and consolidating thedeposition layer. Such embodiments can utilize known OVD techniques toapply the deposition layer.

[0277] Other methods of forming the optical fiber preform are compatiblewith embodiments of the present invention. In certain embodiments, thesol-gel-derived rod 1620 comprises pure silica, while in otherembodiments, the sol-gel-derived rod 1620 comprises silica doped to havea predetermined refractive index profile, to provide photosensitivity,or to provide amplification of optical signals. Examples of dopantsinclude, but are not limited to, germanium, fluorine, aluminum, boron,tin, phosphorous, erbium, and rare earth elements.

[0278] In certain embodiments in which the sol-gel-derived rod 1620comprises a cylindrical core portion and a tubular cladding portion, thetubular cladding portion is around and concentric with the core portion.The cladding portion of certain such embodiments has a refractive indexwhich is between approximately 0.3% and approximately 0.4% less than therefractive index of the core portion. As described above, thesol-gel-derived rod 1620 can be fabricated by a multiple casting processin which a cladding gel is formed by allowing a first sol-gel solutionto gel while confined to a predetermined tubular volume, and allowing asecond sol-gel solution to gel while confined to a predetermined innervolume within the tubular volume. In certain such embodiments, the ratioof the diameter of the core portion to the diameter of the claddingportion is less than approximately ½.

[0279] In certain embodiments, the substrate portion 1630 of the opticalfiber preform 1640 has a refractive index which is between approximately0.3% and approximately 0.4% less than the refractive index of thesol-gel-derived rod 1620. The ratio of the diameter D₂ of thesol-gel-derived rod 1620 to the diameter D₃ of the substrate portion1630 in certain embodiments is between approximately 4/125 andapproximately 10/125, corresponding to a single-mode optical fiber. Inother embodiments, the ratio of D₂/D₃ is between approximately 50/125and approximately 100/140, corresponding to a multiple-mode opticalfiber.

[0280] In certain embodiments in which the optical fiber preform 1640comprises a sleeve portion 1642, the ratio of the diameter D₂ of thesol-gel-derived rod 1620 to the diameter D₄ of the optical fiber preform1640 is between approximately 4/125 and approximately 10/125,corresponding to a single-mode optical fiber. In other embodiments, theratio of D₂/D₄ is between approximately 50/125 and approximately100/140, corresponding to a multiple-mode optical fiber.

[0281] The optical fiber preform 1640 fabricated in accordance withembodiments of the present invention can be drawn in accordance withprior art methods to form an optical fiber. The properties of theresultant optical fiber are dependent upon the fabrication process usedto form the optical fiber preform 1640. In certain embodiments, theresultant optical fiber has a mode-field diameter D_(mf) wherein theratio of D_(mf) to the outer diameter of the optical fiber is betweenapproximately 4/125 and approximately 12/125.

[0282] Forming Doped Sol-Gel Materials

[0283] In certain embodiments, it is desirable to use dopants to modifythe optical properties of the resultant glass monoliths. For example,the optical properties of optical fibers depend on the refractiveindices of the core and cladding portions, which can be tailored byusing appropriate dopants at appropriate concentrations. As anotherexample, dopants can be used to generate sol-gel materials which arephotosensitive (i.e. have refractive indices which can be modified byirradiation). Furthermore, in other embodiments, dopants withappropriate fluorescence properties (e.g., erbium or other rare earthelements) can be used to produce optical fiber amplifiers.

[0284] One characteristic of the performance of an optical fiber is itsnumerical aperture, which is an expression of the light gatheringability of the fiber (i.e., its ability to accept non-normal incidentrays in its bound modes). Optical fibers with large numerical apertureshave utility as multimode optical fibers, as well as increased capacity,lower operation costs, and lower costs for related optical components.

[0285] The dependence of the numerical aperture (“NA”) on the refractiveindices of the core (“n_(core)”) and cladding (“n_(clad)”) is estimatedby the equation: NA=(n_(core) ²−n_(clad) ²)^(1/2). By increasingn_(core), by decreasing n_(clad), or by a combination of the two, thenumerical aperture of the optical fiber can be increased. Doping withappropriate dopants (e.g., fluorine or boron) can decrease therefractive index (sometimes referred to as “down doping”), as comparedto the refractive index of pure silica. Doping with other appropriatedopants (e.g., germanium, phosphorous, aluminum, titanium, or zirconium)can increase the refractive index, as compared to the refractive indexof pure silica. In addition, appropriate dopants (e.g., tin) can be usedto provide a photosensitive optical fiber.

[0286]FIG. 33 schematically illustrates the dependence of the refractiveindex of fluorine-doped silica glass as a function of fluorineconcentration for an exemplary system. The refractive index decreaseswith increasing fluorine concentration, reaching a minimum dependent onthe system. In certain systems, the minimum refractive index occurs atapproximately 8 wt. % of fluorine. Further increases of the fluorineconcentration result in less reduction of the refractive index ascompared to pure silica glass. Therefore, to provide reduced-indexsilica glass, it is desirable to dope silica glass with fluorine tomaximize the reduction of the refractive index.

[0287] Standard chemical vapor deposition techniques have been usedpreviously to introduce fluorine or other index-reducing elements in thecladding portions of optical fiber preforms. However, the highestfluorine percentages achieved by such processes have been approximately4 wt. %, which provides a numerical aperture of approximately 0.22 whenused in a doped cladding portion with a pure silica core portion. Forexample, Heraeus Tenevo AG of Hanau, Germany sells Fluosil® preforms,manufactured using plasma outside deposition, which have claddingportions with 4.0 wt. % fluorine. The fluorine concentrations achievableby such gas-phase deposition processes are limited due to the volatilityof the fluorine-containing compounds.

[0288] To achieve larger numerical apertures, the core portion can bedoped with germanium or other index-increasing elements. However, thesedopants can be expensive and can introduce structural changes or otherdamage to the core portion. Since the core portion carries the majorityof the optical power transmitted through the optical fiber, it istherefore often desirable to avoid dopant-related damage of the coreportion by further reducing the refractive index of the claddingportion.

[0289]FIG. 34 is a flow diagram of a method 2100 of preparing a solutionfor forming a doped gel monolith in accordance with embodiments of thepresent invention. In an optical preform comprised of a plurality ofmaterial components including a core material and a cladding material, acomponent can be manufactured by the process described in FIG. 34. Whilethe flow diagram of FIG. 34 illustrates a particular embodiment withsteps in a particular order, other embodiments with different orders ofsteps are also compatible with the present invention.

[0290] In the embodiment described in FIG. 34, in an operational block2110, a first substance is provided, the first solution comprising ametal alkoxide. In an operational block 2120, a second substance isprovided, the second substance comprising a catalyst. In an operationalblock 2130, a chemical comprised of a dopant is provided. In anoperational block 2140, a solution comprising the dopant is formed, saidforming comprising mixing the first substance and the second substancetogether. In an operational block 2150, the solution is cooled to amixture temperature which is substantially below room temperature. Thesolution has a significantly longer gelation time at the mixturetemperature than at room temperature.

[0291] Examples of metal alkoxides compatible with embodiments of thepresent invention include, but are not limited to, silicon alkoxides(such as tetramethylorthosilicate (TMOS) or tetraethylorthosilicate(TEOS)), aluminum alkoxides, zirconium alkoxides, and titaniumalkoxides. In certain embodiments, the first substance comprises morethan one metal alkoxide. In certain embodiments, the first substancefurther comprises a solvent. Examples of solvents include, but are notlimited to, alcohols (e.g., ethyl alcohol, methyl alcohol, isopropanol,or other reagent alcohols). The first substance in certain embodimentscomprises a plurality of substances in liquid form (e.g., a solution oftwo or more substances), while in other embodiments, it is a powder.

[0292] Examples of catalysts include, but are not limited to,hydrofluoric acid (HF) an ammonia (NH₃). In certain embodiments, thesecond substance further comprises a solvent, examples of which include,but are not limited to alcohols (e.g., ethyl alcohol, methyl alcohol,isopropanol, or other reagent alcohols). The second substance in certainembodiments comprises a plurality of substances (e.g., a solution of twoor more substances), while in other embodiments, it is a singlesubstance.

[0293] Examples of chemicals comprised of a dopant include, but are notlimited to, germanium alkoxides (e.g., tetraethoxygermane (TEOG)),fluorine-containing chemicals (e.g., triethoxyfluorosilane,trimethoxyfluorosilane, tripropyloxyfluorosilane, HF, LiF, and AlF₃),tin-containing chemicals (e.g., SnCl₄, Sn(OPr)₄, and Sn(But)₂(OOCCH₃)₂,boron-containing chemicals (e.g., B[OC₂H₅]₃), and phosphorous-containingchemicals (e.g., POCl₃, H₃PO₄, and PO[OC₂H₅]₃). In addition, using aplurality of dopants is compatible with certain embodiments.

[0294] In certain embodiments, the chemical comprised of the dopant issubstantially free of fluorine-containing alkoxide. The catalyst ofcertain such embodiments comprises a fluorine-containing chemical (e.g.,HF) while the chemical comprised of the dopant is substantiallyfluorine-free (e.g. TEOG). The resultant glass monolith of suchembodiments will be doped with both fluorine and germanium.

[0295] In certain embodiments, the first substance comprises thechemical, in other embodiments, the second substance comprises thechemical, and in still other embodiments, both the first substance andsecond substance comprise the chemical. In still other embodiments, thechemical is added to the mixed first and second substances.

[0296] FIGS. 35A-C are flow diagrams of various embodiments of theoperational block 2140. In the embodiment described in FIG. 35A, formingthe solution comprises mixing the first substance and the chemicaltogether in an operational block 2141, thereby forming a doped firstsubstance. In such embodiments, the doped first substance is mixed withthe second substance in an operational block 2142 to form the solutioncomprising the dopant.

[0297] In the embodiment described in FIG. 35B, forming the solutioncomprises mixing the second substance and the chemical together in anoperational block 2143, thereby forming a doped second substance. Insuch embodiments, the doped second substance is mixed with the firstsubstance in an operational block 2144 to form the solution comprisingthe dopant.

[0298] In the embodiment described in FIG. 35C, forming the solutioncomprises mixing the first substance and second substance in anoperational block 2145, then mixing the chemical with the mixed firstand second substances in an operational block 2146. In certain suchembodiments, upon mixing, the first and second substances begin toundergo gelation. If gelation is permitted to proceed prior to theaddition of the chemical, incorporation of the dopant in the gelmonolith may be incomplete and the resultant gel monolith may not havethe desired dopant concentration. In certain embodiments, the chemicalis mixed with the first and second substances concurrently with mixingthe first and second substances together. In other embodiments, thechemical is mixed with the first and second substances at least 5minutes prior to completion of gelation of the mixed first and secondsubstances.

[0299] In addition, in certain embodiments, the catalyst comprises thechemical. For example, where the catalyst comprises hydrofluoric acid,the catalyst can also serve as the chemical comprised of the dopant. Insuch embodiments, because the second substance already comprises HF, thechemical does not have to be added to the first substance, secondsubstance, or the solution.

[0300] While in certain embodiments, the second substance furthercomprises water, in other embodiments, water is added to the solutionsuch that the solution thereby comprises water and metal alkoxide. Thesolution can then begin to undergo the hydrolysis and polymerizationreactions which form the gel. The presence of the catalyst in thesolution accelerates the formation of the gel (i.e., reduces thegelation time of the solution as compared to the gelation time withoutthe catalyst) as described above. In addition, in embodiments in whichHF is used as the catalyst, the HF can contribute to the fluorineconcentration of the resultant glass monolith.

[0301] The solution is cooled to a mixture temperature substantiallybelow room temperature in the operational block 2150. In certainembodiments (e.g., in which the chemical comprised of the dopantcomprises a fluorine-containing alkoxide), the mixture temperature isbelow zero degrees Celsius. Such mixture temperatures serve to slow theformation of the gel, such that the solution has a significantly longergelation time at the mixture temperature than at room temperature. Thegelation time of the solution is extended by keeping the solution at thepredetermined temperature below room temperature. The solution can thenbe allowed to gel, thereby forming a doped gel monolith.

[0302] In certain embodiments, only the solution is cooled to achievethe mixture temperature. In other embodiments, the solution is cooled bycooling the first substance prior to mixing the first and secondsubstances together. In still other embodiments, the solution is cooledby cooling the second substance prior to mixing the first and secondsubstances together. In still other embodiments, the solution is cooledby cooling the chemical comprised of the dopant.

[0303] In this way, in certain embodiments, achieving a reduced mixturetemperature makes it possible to increase the catalyst concentration inthe solution while reducing the problematic effects associated withhigher catalyst concentrations. Similarly, in other embodiments in whichthe chemical speeds up the gelation reaction, achieving a reducedmixture temperature makes it possible to increase the dopantconcentration in the solution while avoiding the problems of prematuregelation. Furthermore, in certain embodiments, the reduced mixturetemperature affects the gelation rates of the metal alkoxide and thedopant-containing alkoxide (e.g., TEOG), so that the gelation rates aremore closely matched to facilitate homogeneous incorporation of thedopant in the resultant gel monolith.

[0304] Described below are various aspects and examples of embodimentsfor forming gel monoliths doped with fluorine, germanium, or tin. Otherembodiments utilizing various other dopants are also compatible with thepresent invention.

[0305] Fluorine-Doped Gel Monoliths

[0306] In certain embodiments in which the chemical comprised of thedopant comprises a fluorine-containing chemical, the solution preferablycomprises at least 1 mole %, more preferably at least 4 mole %, and mostpreferably at least 8 mole % of the fluorine-containing chemical. Upongelation, drying, and consolidation of the fluorine-doped gel monolith,certain embodiments result in a fluorine-doped silica glass withpreferably more than approximately 4 wt. % fluorine, and more preferablybetween approximately 6 wt. % fluorine and approximately 10 wt. %fluorine. For 1550 nm light, the refractive index of the fluorine-dopedsilica glass of certain embodiments is preferably at least approximately0.3%, more preferably between approximately 0.3% and approximately 3%,and most preferably between approximately 1% and 3% lower than therefractive index of pure silica glass.

[0307] In certain embodiments for doping the silica glass with afluorine-containing alkoxide, the solution further comprises hydrogenfluoride (HF) to impede decomposition of the fluorine-containingalkoxide. For example, triethoxyfluorosilane (F—Si(OEt)₃) can decomposein the following reactions: F—Si(OEt)₃+H₂O→HF+Si(OEt)₃OH orF—Si(OEt)₃+ethanol→HF+TEOS. The inclusion of HF to the solution impedesthis decomposition reaction during gelation. This utility of HF is inaddition to its utility as a catalyst for the hydrolysis andpolymerization reactions during gelation. As described above forembodiments in which HF is included in the solution as a catalyst,reducing the mixture temperature is helpful in embodiments in which HFis included in the solution to impede the decomposition reaction.

[0308] While heating the fluorine-doped monolith to high temperaturesduring the consolidation process, the fluorine-doped monolith can reactwith oxygen or chlorine molecules to decompose and generate gases (suchas SiOClF or SiCl₂F₂) which liberate fluorine from the fluorine-dopedmonolith. To impede this loss mechanism of fluorine, in certainembodiments, the doped monolith is exposed to a fluorine-containing gasduring the consolidation process to impede the decomposition of fluorinefrom the silica glass. In certain such embodiments, the consolidationfurnace is backfilled with a fluorine-containing gas during theconsolidation process. The fluorine-containing gas can also providefluorine atoms which replace OH radicals in the structure of the gelmonolith. Examples of fluorine-containing gases compatible withembodiments of the present invention include, but are not limited to,silicon tetrafluoride (SiF₄) or sulphur hexafluoride (SF₆).

EXAMPLE 3 Fluorine-Doped Tubular Gel Monolith

[0309] In an exemplary embodiment of the present invention, a firstsubstance is prepared by mixing approximately 1247 grams (6.5 moles) oftriethoxyfluorosilane (TEOF) of 95% purity, approximately 4066 grams(19.5 moles) of tetraethylorthosilicate (TEOS), and approximately 3833grams (83 moles) of reagent alcohol. A second substance is prepared bymixing approximately 848 grams (47 moles) of deionized water,approximately 104 grams of 50% HF solution (2.6 moles of HF), andapproximately 958 grams (21 moles) of reagent alcohol. Both the firstand second substances are stored at approximately −80° C. forapproximately 24 hours and the mixing bath is maintained atapproximately −10° C.

[0310] The second substance is added to the first substance withinapproximately one minute with continuous stirring, to form the solution.After stirring for approximately 9 minutes more, the resultinghomogeneously translucent solution is filtered using a 0.1 μm filter,and is cast into at least one cylindrical mold having a removabletubular insert as described above. The solution is allowed to gel forapproximately 10 minutes, at which point, a thin layer of reagentalcohol is placed on the gel to protect the gel from excessive dryingand cracking due to contact with air. Approximately 30 minutes aftergelation, the tubular insert is removed, and the resultant bubble- andparticle-free tubular wet gel monolith is aged at room temperature(approximately 26° C.) for approximately three days.

[0311] The tubular wet gel monolith is then dried using the temporaltemperature profile procedure described above at approximately oneatmosphere and at temperatures less than approximately 200° C. Incertain embodiments, the temporal temperature profile is tailored toprovide a resultant pore diameter distribution with a mean pore diameterin the range from approximately 300 Å to 800 Å.

[0312] The dried tubular gel monolith is then transferred to the hightemperature furnace for consolidation by ramping the temperature to atemperature above 1200° C. Remaining organic and solvent moleculesadsorbed on the surfaces of the gel monolith can be burned off byheating to a temperature at approximately 400-500° C. in an atmosphereof nitrogen and oxygen.

[0313] To reduce the loss of fluorine from the gel monolith during theconsolidation process, a mixture of SiF₄ and helium is introduced in thefurnace upon reaching a temperature of approximately 400-500° C.Immediately before gel densification, the SiF₄ flow can be stopped andthe helium flow continued while the gel becomes fully densified attemperatures above 1200° C. After consolidation, the tubular monolith iscooled down to room temperature, and the surfaces prepared for furtherpreform manufacturing.

[0314] Non-Fluorine-Doped Gel Monoliths

[0315]FIG. 36 is a flow diagram of a method 2200 of forming a doped gelmonolith in accordance with other embodiments of the present invention.In an optical preform comprised of a plurality of material componentsincluding a core material and a cladding material, a component can bemanufactured by the process described in FIG. 36. While the flow diagramof FIG. 36 illustrates a particular embodiment with steps in aparticular order, other embodiments with different orders of steps arealso compatible with the present invention.

[0316] In the embodiment described in FIG. 36, in an operational block2210, a first substance is provided, the first substance comprising ametal alkoxide. In an operational block 2220, a second substance isprovided, the second substance comprising a catalyst. In an operationalblock 2230, a chemical comprised of a dopant is provided, the chemicalbeing substantially free of fluorine-containing alkoxide. In anoperational block 2240, a solution comprising the dopant andsubstantially free of fluorine-containing alkoxide is formed. Theforming of the solution comprises mixing the first substance and thesecond substance together. In an operational block 2250, the solution iscooled to a mixture temperature substantially below room temperature.The solution of such embodiments has a significantly longer gelationtime at the mixture temperature than at room temperature. In anoperational block 2260, the solution is allowed to gel, thereby formingthe doped gel monolith.

[0317] In certain embodiments in which the chemical comprised of thedopant comprises a germanium-containing alkoxide, the solutionpreferably comprises at least 1 mole % of the germanium-containingalkoxide. Upon gelation, drying, and consolidation of thegermanium-doped gel monolith, certain embodiments result in agermanium-doped silica glass with preferably more than approximately 4wt. % germanium, and more preferably between approximately 5 wt. %germanium and approximately 10 wt. % germanium. For 1550 nm light, therefractive index of the germanium-doped silica glass of certainembodiments is preferably at least approximately 0.3%, and morepreferably between approximately 0.3% and approximately 0.4% higher thanthe refractive index of pure silica glass.

EXAMPLE 4 Germanium-Doped Tubular Gel Monolith

[0318] In another exemplary embodiment of the present invention, a firstsubstance is prepared by mixing approximately 177 grams (0.7 moles) oftetraethoxygermane (TEOG), approximately 1937 grams (9.3 moles) oftetraethylorthosilicate (TEOS), and approximately 921 grams (20 moles)of reagent alcohol. A second substance is prepared by mixingapproximately 319 grams (17.7 moles) of deionized water, approximately100 grams of 50% HF solution (2.5 moles of HF), and approximately 230grams (5 moles) of reagent alcohol. Both the first and second substancesare stored at approximately −30° C. for approximately 24 hours and themixing bath is maintained at approximately −10° C.

[0319] The second substance is added to the first substance withinapproximately one minute with continuous stirring, to form the solution.After stirring for approximately 9 minutes more, the resultinghomogeneously translucent solution is filtered using a 0.1 μm filter,and is cast into at least one cylindrical mold having a removabletubular insert as described above. The solution is allowed to gel forapproximately 20-30 minutes, at which point, a thin layer of reagentalcohol is placed on the gel to protect the gel from excessive-dryingand cracking due to contact with air. Approximately 30 minutes aftergelation, the tubular insert is removed, and the resultant bubble- andparticle-free tubular wet gel monolith is aged at room temperature(approximately 26° C.) for approximately three days.

[0320] The tubular wet gel monolith is then dried using the temporaltemperature profile procedure described above at approximately oneatmosphere and at temperatures less than approximately 200° C. Incertain embodiments, the temporal temperature profile is tailored toprovide a resultant pore diameter distribution with a mean pore diameterin the range from approximately 500 Å to 700 Å.

[0321] The dried tubular gel monolith is then transferred to the hightemperature furnace for consolidation by ramping the temperature to atemperature above 1300° C. Remaining organic and solvent moleculesadsorbed on the surfaces of the gel monolith can be burned off byheating to a temperature at approximately 400-700° C. in an atmosphereof nitrogen and oxygen. An atmosphere of chlorine, oxygen, and heliumcan be applied for deep cleaning at a temperature between approximately800° C. and approximately 1000° C. In this way, the OH concentration canbe controlled to be below approximately 10 ppb.

[0322] To remove any remaining chlorine from the gel monolith, a mixtureof oxygen and helium is introduced in the consolidation furnace uponreaching a temperature of approximately 1000° C. Immediately before geldensification, the oxygen flow can be stopped and the helium flowcontinued while the gel becomes fully densified at temperatures above1300° C. After consolidation, the tubular monolith is cooled down toroom temperature, and the surfaces prepared for further preformmanufacturing.

EXAMPLE 5 Tin and Phosphorous Co-Doped Gel Monolith

[0323] In another exemplary embodiment of the present invention, a firstsubstance is prepared by mixing approximately 16.7 grams (0.047 moles)of Sn(OPr)₄, 124 grams (0.68 moles) of PO(OEt)₃, 1251 grams (6.0 moles)of TEOS, and 808 grams (13.4 moles) of isopropanol. A second substanceis prepared by mixing approximately 204 grams (11.3 moles) of deionizedwater, 71.5 grams (1.68 moles) of HF (47%), and 202 grams (3.4 moles) ofisopropanol. Both the first and second substances are stored atapproximately −30 ° C. for approximately 24 hours and the mixing bath ismaintained at approximately −10° C. In certain other embodiments inwhich the chemical comprised of the dopant comprises a tin-containingchemical, the solution preferably comprises at least 0.1 mole % of thetin-containing chemical. In certain other embodiments in which thechemical comprised of the dopant comprises a phosphorous-containingchemical, the solution preferably comprises at least 1 mole % of thephosphorous-containing chemical.

[0324] The second substance is added to the first substance withinapproximately one minute with continuous stirring, to form the solution.After stirring for approximately 9 minutes more, the resultinghomogeneously translucent solution is filtered using a 0.6 μm filter,and is cast into at least one cylindrical mold as described above. Thesolution is allowed to gel for approximately 30 minutes, at which point,a thin layer or reagent alcohol is placed on the gel to protect the gelfrom excessive drying and cracking due to contact with air. The gel isaged at room temperature (approximately 26° C.) for approximately threedays.

[0325] The wet gel is then dried using the temporal temperature profileprocedure described above at approximately one atmosphere and attemperatures less than approximately 200° C. In certain embodiments, thetemporal temperature profile is tailored to provide a resultant porediameter distribution with a mean pore diameter in the range fromapproximately 500 Å to 700 Å.

[0326] The dried gel monolith is then transferred to the hightemperature furnace for consolidation. The remaining solvents andorganics adsorbed on the surfaces of the gel monolith can be burned offby heating to a temperature at approximately 400-700° C. in anatmosphere of nitrogen and oxygen. An atmosphere of chlorine, oxygen,and helium can be applied for deep cleaning at a temperature betweenapproximately 700° C. and approximately 900° C., followed by oxidationat approximately 1000° C. The monolith is fully densified by heating attemperatures of approximately 1250° C.

EXAMPLE 6 Boron-Doped Gel Monolith

[0327] In another exemplary embodiment of the present invention, a firstsubstance is prepared by mixing approximately 230 grams (1.3 moles) ofB(OEt)₃, 1173 grams (5.6 moles) of TEOS, and 633 grams (13.8 moles) ofreagent alcohol. A second substance is prepared by mixing approximately208 grams (11.6 moles) of deionized water, 68.8 grams (1.7 moles) of HF(50%), and 158 grams (3.4 moles) of reagent alcohol. Both the first andsecond substances are stored at approximately −30° C. for approximately24 hours and the mixing bath is maintained at approximately −10° C. Incertain other embodiments in which the chemical comprised of the dopantcomprises a boron-containing chemical, the solution preferably comprisesat least 1 mole % of the boron-containing chemical.

[0328] The second substance is added to the first substance withinapproximately one minute with continuous stirring, to form the solution.After stirring for approximately 9 minutes more, the resultinghomogeneously translucent solution is filtered using a 0.6 μm filter,and is cast into at least one cylindrical mold as described above. Thesolution is allowed to gel for approximately 40 minutes, at which point,a thin layer or reagent alcohol is placed on the gel to protect the gelfrom excessive drying and cracking due to contact with air. The gel isaged at room temperature (approximately 26° C.) for approximately threedays.

[0329] The wet gel is then dried using the temporal temperature profileprocedure described above at approximately one atmosphere and attemperatures less than approximately 200° C. In certain embodiments, thetemporal temperature profile is tailored to provide a resultant porediameter distribution with a mean pore diameter in the range fromapproximately 400 Å to 600 Å.

[0330] The dried gel monolith is then transferred to the hightemperature furnace for consolidation. The remaining solvents andorganics adsorbed on the surfaces of the gel monolith can be burned offby heating to a temperature at approximately 300-600° C. in anatmosphere of nitrogen and oxygen. An atmosphere of chlorine and oxygencan be applied for deep cleaning at a temperature below approximately775° C., followed by oxidation at approximately 775° C. forapproximately 10 hours. The monolith is fully densified by heating attemperatures of approximately 1200° C.

[0331] Forming Tubular Gel Monoliths

[0332] As mentioned above in relation to casting a gel monolith, incertain embodiments, a tubular gel monolith is formed which undergoesadditional processing to form a sol-gel-derived tube. FIG. 37 is a flowdiagram corresponding to a method 2300 of forming a tubular gel monolithin accordance with embodiments of the present invention. In anoperational block 2310, a sol-gel solution is prepared, the sol-gelsolution comprising at least 3 mole % of a catalyst. In an operationalblock 2320, a tubular wet gel monolith is formed by allowing the sol-gelsolution to undergo gelation. In an operational block 2330, the tubularwet gel monolith is dried and shrunk by exposing the tubular wet gelmonolith to a temporal temperature profile, thereby forming the tubularxerogel monolith.

[0333] Embodiments of the method 2300 of forming a tubular gel monolithcomprise operational blocks which are similar to those of embodiments ofthe above-described formation of a sol-gel-derived rod as the coreportion of an optical fiber preform. Similarly, the tubular gel monolithformed by embodiments of the method 2300 can be used as the claddingportion of an optical preform. Certain embodiments of the presentinvention can thus be considered to be a process for manufacturing atleast one of the components of an optical preform comprised of pluralmaterial components including a core material and a cladding material.

[0334]FIG. 38 is a flow diagram of the operational block 2310 inaccordance with certain embodiments of preparing the sol-gel solutioncomprising at least 3 mole % of a catalyst. In an operational block2312, a first substance comprising a metal alkoxide is prepared. In anoperational block 2314, a second substance comprising the catalyst isprepared. In an operational block 2316, the first substance and thesecond substance are mixed together, thereby forming the sol-gelsolution. In an operational block 2318, the sol-gel solution is cooledto a mixture temperature substantially below room temperature. Thesol-gel solution has a significantly longer gelation time at the mixturetemperature than at room temperature.

[0335] Embodiments of these operational blocks are described above inrelation to preparing a solution as described in FIGS. 1-8. In certainembodiments, the sol-gel solution comprises at least 1 mole % of thecatalyst. In certain embodiments, the mixture temperature is preferablybelow zero degrees Celsius, more preferably below −10 degrees Celsius,even more preferably below −25 degrees Celsius, and most preferablybelow −40 degrees Celsius. In addition, other embodiments include achemical comprised of a dopant for forming doped gel monoliths, asdescribed above in relation to FIGS. 33-35.

[0336] In certain embodiments, forming the tubular wet gel monolith ofoperational block 2320 comprises confining the sol-gel solution to apredetermined tubular volume while allowing the sol-gel solution toundergo gelation. Exemplary molds compatible with such embodiments aredescribed above in relation to FIGS. 10-16. As described above inrelation to FIG. 16 and FIGS. 11A-D, the predetermined tubular volume450 of certain embodiments is defined by a base 410, a tubular outerwall 420, and a removable tubular insert 430. Confining the firstsol-gel solution 452 to the tubular volume 450 while allowing the firstsol-gel solution 452 to undergo gelation results in a first gel portion404 which is a tubular wet gel monolith.

[0337] In the operational block 2330, the tubular wet gel monolith isdried by exposing the tubular wet gel monolith to a temporal temperatureprofile. Exemplary temporal temperature profiles are described above inrelation to FIGS. 19-26. As described above, this procedure removesliquid from the pores of the tubular wet gel monolith, and the tubularwet gel monolith shrinks in size, resulting in a tubular gel monolith.In certain embodiments, the tubular gel monolith thus formed is thenconsolidated, as described in relation to FIG. 27, thereby forming asol-gel-derived tube.

[0338] In certain embodiments, the tubular wet gel monolith is removedfrom the mold without additional castings, and undergoes additionaldrying and consolidation processing to form a tubular glass monolith.Alternatively, in certain other above-described embodiments, the tubularwet gel monolith is used in further processing whereby a second gelportion 406 is formed within the first gel portion 404. The first andsecond gel portions 404, 406 are then processed further to form astep-index glass monolith. While certain embodiments described abovehave a cylindrical second gel portion formed within the tubular firstgel portion, other embodiments form a tubular second gel portion withinthe tubular first gel portion. Upon further processing, such embodimentsresult in a sol-gel-derived tube comprising a step-index glass.

[0339] In certain embodiments, a central portion is formed within thesol-gel-derived tube. In certain such embodiments, the central portionis formed by the multiple casting process described above in which twogel portions are formed and then undergo drying and consolidation. Inother embodiments, the central portion is formed by applying adeposition layer onto an inner surface of the sol-gel-derived tube andconsolidating the deposition layer. Prior art chemical-vapor-depositionprocesses for the application of the deposition layer are in accordancewith embodiments of the present invention.

[0340] In still other embodiments, the sol-gel-derived tube having afirst diameter undergoes a drawing process whereby its diameter issubstantially reduced to a second diameter less than the first diameter.In certain such embodiments, the central portion is formed by fusing thedrawn tube onto a central rod. In this way, an optical fiber preform canbe formed. Fusing the drawn tube onto the central rod in certainembodiments comprises inserting the central rod into the sol-gel-derivedtube and heating the sol-gel-derived tube. The sol-gel-derived tube iscollapsed onto the central rod and the sol-gel-derived tube and centralrod are annealed.

[0341] In certain embodiments, the central portion has a firstrefractive index and the sol-gel-derived tube has a second refractiveindex. The second refractive index is preferably at least approximately0.3% less than the first refractive index, and more preferably betweenapproximately 0.3% and approximately 0.4% less than the first refractiveindex. In other embodiments (e.g., multi-mode optical fibers), thesecond refractive index is preferably between approximately 1% andapproximately 3% less than the first refractive index.

[0342] In certain embodiments, a sleeve portion is formed around thesol-gel-derived tube. In certain such embodiments, the sleeve portion isformed by the multiple casting process described above in which two gelportions are formed and then undergo drying and consolidation. In otherembodiments, the sleeve portion is formed by applying a deposition layeronto an outer surface of the sol-gel-derived tube and consolidating thedeposition layer. Prior art chemical-vapor-deposition processes for theapplication of the deposition layer are in accordance with embodimentsof the present invention. In still other embodiments, forming the sleeveportion comprises fusing a sleeve tube onto the sol-gel-derived tube.

[0343] Although described above in connection with particularembodiments of the present invention, it should be understood thedescriptions of the embodiments and examples are illustrative of theinvention and are not intended to be limiting. Various modifications andapplications may occur to those skilled in the art without departingfrom the true spirit and scope of the invention as defined in theappended claims.

What is claimed is:
 1. A method of preparing a solution for forming adoped gel monolith, the method comprising: providing a first substancecomprising a metal alkoxide; providing a second substance comprising acatalyst; providing a chemical comprised of a dopant; forming a solutioncomprising the dopant, said forming comprising mixing the firstsubstance and the second substance together; and cooling the solution toa mixture temperature which is at or below zero degrees Celsius, whereinthe solution has a significantly longer gelation time at the mixturetemperature than at room temperature.
 2. The method of claim 1, whereinforming the solution comprises mixing the first substance and thechemical together thereby forming a doped first substance and mixing thesecond substance with the doped first substance.
 3. The method of claim1, wherein forming the solution comprises mixing the second substanceand the chemical together thereby forming a doped second substance andmixing the first substance with the doped second substance.
 4. Themethod of claim 1, wherein forming the solution comprises mixing thechemical with the first and second substances.
 5. The method of claim 4,wherein mixing the chemical with the first and second substances occursconcurrently with mixing the first and second substances together. 6.The method of claim 4, wherein mixing the chemical with the first andsecond substances occurs at least 5 minutes prior to completion ofgelation of the mixed first and second substances.
 7. The method ofclaim 1, wherein cooling the solution comprises cooling the firstsubstance.
 8. The method of claim 1, wherein cooling the solutioncomprises cooling the second substance.
 9. The method of claim 1,wherein cooling the solution comprises cooling the chemical comprised ofthe dopant.
 10. The method of claim 1, wherein the metal alkoxidecomprises tetramethylorthosilicate (TMOS).
 11. The method of claim 1,wherein the metal alkoxide comprises tetramethylorthosilicate (TEOS).12. The method of claim 1, wherein the catalyst comprises the dopant.13. The method of claim 1, wherein the chemical comprised of the dopantcomprises a fluorine-containing chemical.
 14. The method of claim 13,wherein the fluorine-containing chemical comprises a material selectedfrom the group consisting of: triethoxyfluorosilane,trimethoxyfluorosilane, tripropyloxyfluorosilane, HF, LiF, and AlF₃. 15.The method of claim 13, wherein the solution comprises at least 1 mole %of the fluorine-containing chemical.
 16. The method of claim 13, whereinthe solution comprises at least 4 mole % of the fluorine-containingchemical.
 17. The method of claim 13, wherein the solution comprises atleast 8 mole % of the fluorine-containing chemical.
 18. The method ofclaim 13, wherein the fluorine-containing chemical comprises afluorine-containing alkoxide which undergoes a decomposition reaction,and the solution further comprises HF, thereby impeding thedecomposition reaction.
 19. The method of claim 1, wherein the chemicalcomprised of the dopant comprises a germanium-containing alkoxide. 20.The method of claim 19, wherein the germanium-containing alkoxidecomprises tetraethoxygermane (TEOG).
 21. The method of claim 19, whereinthe solution comprises at least 1 mole % of the germanium-containingalkoxide.
 22. The method of claim 1, wherein the chemical comprised ofthe dopant comprises a boron-containing chemical.
 23. The method ofclaim 22, wherein the boron-containing chemical comprises B(OEt)₃. 24.The method of claim 22, wherein the solution comprises at leastapproximately 1 mole % of the boron-containing chemical.
 25. The methodof claim 1, wherein the chemical comprised of the dopant comprises aphosphorous-containing chemical.
 26. The method of claim 25, wherein thephosphorous-containing chemical comprises PO(OEt)₃.
 27. The method ofclaim 25, wherein the solution comprises at least approximately 1 mole %of the phosphorous-containing chemical.
 28. The method of claim 1,wherein the chemical comprised of the dopant comprises a tin-containingchemical.
 29. The method of claim 28, wherein the tin-containingchemical comprises a material selected from the group consisting of:SnCl₄, Sn(OPr)₄, and Sn(But)₂(OOCCH₃)₂.
 30. The method of claim 28,wherein the solution comprises at least approximately 0.1 mole % of thetin-containing chemical.
 31. The method of claim 1, wherein the firstsubstance further comprises a solvent.
 32. The method of claim 31,wherein the solvent comprises alcohol.
 33. The method of claim 1,wherein the catalyst comprises hydrofluoric acid.
 34. The method ofclaim 33, wherein the chemical comprised of the dopant compriseshydrofluoric acid.
 35. The method of claim 1, wherein the secondsubstance further comprises water.
 36. A method of forming a doped gelmonolith, the method comprising: preparing a solution using the methodof claim 1; and allowing the solution to gel, thereby forming the dopedgel monolith.
 37. The method of claim 36, wherein the doped gel monolithis fluorine-doped.
 38. The method of claim 37, wherein the doped gelmonolith has more than approximately 4 wt. % fluorine.
 39. The method ofclaim 37, wherein the doped gel monolith has between approximately 6 wt.% fluorine and approximately 10 wt. % fluorine.
 40. A doped gel monolithformed by the method of claim
 36. 41. A method of forming a doped glassmonolith, the method comprising: forming a doped gel monolith using themethod of claim 36; drying the doped gel monolith, and consolidating thedoped gel monolith, thereby forming the doped glass monolith.
 42. Themethod of claim 41, wherein the doped glass monolith comprisesfluorine-doped silica glass.
 43. The method of claim 42, whereinconsolidating the doped gel monolith comprises exposing the doped gelmonolith to a fluorine-containing gas.
 44. The method of claim 43,wherein the fluorine-containing gas comprises SiF₄ or SF₆.
 45. Themethod of claim 42, wherein the refractive index of the fluorine-dopedsilica glass for 1550 nm light is at least approximately 0.3% lower thanthe refractive index of pure silica glass.
 46. The method of claim 42,wherein the refractive index of the fluorine-doped silica glass for 1550nm light is between approximately 0.3% and approximately 3% lower thanthe refractive index of pure silica glass.
 47. The method of claim 42,wherein the refractive index of the fluorine-doped silica glass for 1550nm light is between approximately 1% and 3% lower than the refractiveindex of pure silica glass.
 48. A method of processing a solutioncomprising a catalyst, water, metal alkoxide, and a chemical comprisedof a dopant, the method comprising extending a gelation time of thesolution by keeping the solution at a predetermined temperature at orbelow zero degrees Celsius.
 49. A component of an optical preformcomprised of a plurality of material components including a corematerial and a cladding material, the component manufactured by theprocess of: providing a first substance comprising a metal alkoxide;providing a second substance comprising a catalyst; providing a chemicalcomprised of a dopant; forming a solution comprising the dopant, saidforming comprising mixing the first substance and the second substancetogether; and cooling the solution to a mixture temperature at or belowzero degrees Celsius, wherein the solution has a significantly longergelation time at the mixture temperature than at room temperature.
 50. Amethod of forming a doped gel monolith, the method comprising: providinga first substance comprising a metal alkoxide; providing a secondsubstance comprising a catalyst; providing a chemical comprised of adopant, said chemical being substantially free of fluorine-containingalkoxide; forming a solution substantially free of fluorine-containingalkoxide and comprising the dopant, said forming comprising mixing thefirst substance and the second substance together; cooling the solutionto a mixture temperature substantially below room temperature, whereinthe solution has a significantly longer gelation time at the mixturetemperature than at room temperature; and allowing the solution to gel,thereby forming the doped gel monolith.
 51. The method of claim 50,wherein forming the solution comprises mixing the first substance andthe chemical together thereby forming a doped first substance and mixingthe second substance with the doped first substance.
 52. The method ofclaim 50, wherein forming the solution comprises mixing the secondsubstance and the chemical together thereby forming a doped secondsubstance and mixing the first substance with the doped secondsubstance.
 53. The method of claim 50, wherein forming the solutioncomprises mixing the chemical with the first and second substances. 54.The method of claim 53, wherein mixing the chemical with the first andsecond substances occurs concurrently with mixing the first and secondsubstances together.
 55. The method of claim 53, wherein mixing thechemical with the first and second substances occurs at least 5 minutesprior to completion of gelation of the mixed first and secondsubstances.
 56. The method of claim 50, wherein cooling the solutioncomprises cooling the first substance.
 57. The method of claim 50,wherein cooling the solution comprises cooling the second substance. 58.The method of claim 50, wherein cooling the solution comprises coolingthe chemical comprised of the dopant.
 59. The method of claim 50,wherein the metal alkoxide comprises tetramethylorthosilicate (TMOS).60. The method of claim 50, wherein the metal alkoxide comprisestetraethylorthosilicate (TEOS).
 61. The method of claim 50, wherein thechemical comprised of the dopant comprises a germanium-containingalkoxide.
 62. The method of claim 61, wherein the germanium-containingalkoxide comprises tetraethoxygermane (TEOG).
 63. The method of claim50, wherein the chemical comprised of the dopant comprises aboron-containing chemical.
 64. The method of claim 63, wherein theboron-containing chemical comprises B(OEt)₃.
 65. The method of claim 63,wherein the solution comprises at least approximately 1 mole % of theboron-containing chemical.
 66. The method of claim 50, wherein thechemical comprised of the dopant comprises a phosphorous-containingchemical.
 67. The method of claim 66, wherein the phosphorous-containingchemical comprises PO(OEt)₃.
 68. The method of claim 66, wherein thesolution comprises at least approximately 1 mole % of thephosphorous-containing chemical.
 69. The method of claim 50, wherein thechemical comprised of the dopant comprises a tin-containing chemical.70. The method of claim 69, wherein the tin-containing alkoxidecomprises a material selected from the group consisting of: SnCl₄,Sn(OPr)₄, and Sn(But)₂(OOCCH₃)₂.
 71. A component of an optical preformcomprised of a plurality of material components including a corematerial and a cladding material, the component manufactured by theprocess of: providing a first substance comprising a metal alkoxide;providing a second substance comprising a catalyst; providing a chemicalcomprised of a dopant, said chemical being substantially free offluorine-containing alkoxide; forming a solution substantially free offluorine-containing alkoxide and comprising the dopant, said formingcomprising mixing the first substance and the second substance together;cooling the solution to a mixture temperature substantially below roomtemperature, wherein the solution has a significantly longer gelationtime at the mixture temperature than at room temperature; and allowingthe solution to gel, thereby forming a gel monolith.